MPH 08
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Esra AllamMPH 08
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Esra AllamUNIT-1
Basic Properties of Nucleus
Structure of the Unit
1.0 Objectives
1.1 Introduction
1.2 Nuclear Radius and Nuclear Density
1.3 Nuclear Spin (Total Angular Momentum)
1.4 Parity
1.5 Illustrative Examples
1.6 Self Learning Exercise-I
1.7 Magnetic Moment
1.8 Binding Energy
1.9 Semiempirical Mass Formula
1.10 Illustrative Examples
1.11 Self Learning Exercise-II
1.12 Summary
1.13 Glossary
1.14 Answers to Self Learning Exercises
1.15 Exercise
1.16 Answers to Exercise
References and Suggested Readings
1.0
1.0Objectives
Objectives
In this unit ,we shall describe the certain basic properties of nucleus such as size,
mass, angular momentum, magnetic moment ,electric quadrupole moment etc. and
try to understand them by means of elementary theories.
1
1.1
1.1Introduction
Introduction
Main properties of atoms, molecules, solids and liquids can be explained on the
basis of behavior of the electrons, nevertheless, role of the nucleus is important in
nature. Applications of nuclear physics have had enormous effects on mankind.
The most spectacular application of nuclear physics is nuclear energy .The energy
characteristic of atoms is of the order of eV whereas of nucleus is of the order of
MeV . In this unit we introduce some of its most basic properties. In the last we
shall describe the semiempirical mass formula by employing liquid drop model.
1.2
1.2Nuclear
NuclearRadius
Radiusand
andNuclear
NuclearDensity
Density
The size of nucleus was first investigated in the particle scattering experiments
of Rutherford. In this experiment, the distance of closest approach provides the
information about the nuclear radius of the order of 10–14m.
The most accurate results involve scattering of high energy relativistic electrons (of
about 200 MeV kinetic energy) from thin target of the material under study. The
electrons having such high energies have wavelengths comparable with the radius
of nucleus. As nuclear forces do not act on an electron, so we have advantage with
electrons that their electromagnetic interaction with the nucleus (nuclear charge) is
well known. Thus electron scattering tells us the distribution of charge. If highly
energetic neutrons are used as the scattering particles, then neutron scattering tells
us the distribution of nuclear mass because neutron interacts only through the
nuclear forces. If we assume a nucleus is an approximately spherically symmetric,
we may express its size in terms of its radius R. Nuclear radius is measured in
femtometer.
1 femtometer= 1 Fermi = 1 fm= 10–15m
The experimental results indicate that the radius R varies approximately as the
cube root of the mass number and this relationship is usually expressed as
R R0 A1/ 3 (1)
where A is the mass number and R0 is an empirical coefficient and its approximate
value is
R0 ≈ 1.2 × 10 –15m
Actual value of R0 depends on the technique that used for determination of nuclear
radius.
2
4 3
Nuclear Volume V
3
R .From eq.(1) we have
4 3
V
3
R0 A (2)
i.e. volume of a nucleus is proportional to the number of nucleons.
As the masses of a proton and a neutron are approximately equal, say mp , then
mass of nucleus m may be written as
m=mpA (3)
mp
Nuclear mass density m m 4
V R03
3
which is independent of mass number A i.e. the mass density is approximately
same for all nuclei.
We have mp=1.67 × 10−27kg and R 0 1.2x10 15 m
1.67 1027 kg
Therefore m 4 2.3 1017
2 10 15 3 m3
3
i.e. nuclear mass density is of the order of 1017 kg3 . Thus we find that density of a
m
nucleus has the extremely high value, neutron stars have densities of this
magnitude.
Number of nucleons per unit volume = Mass Density
Mass of a nucleus
17
2 .3 10
27
1044 nucleons/m3
1.6 10
Experimental observations for all nuclei are reasonably well approximated by
following nuclear charge distribution (nuclear charge density):
0
(r ) (4)
(r R )
1 exp
t
Above empirical equation represents Fermi two parameter model, where 0 is the
nucleon charge density near the centre of the nucleus and r is radial distance.
At distance r=R, from eq.(4) we have
0
(r ) 0
1 1 2
3
i.e. R is the radius at which the density has fallen to half its central value. Term t is
nuclear surface thickness parameter. The distance over which nuclear charge
density (r) falls from 0.9 0 to 0.1 0 is 4.4 t.
We can prove this by using eq.(4)
0 r1 R
0 .9 0 ln 9 (5)
r R t
1 exp 1
t
0 r2 R
and 0 .1 0 n9 (6)
r R t
1 exp 2
t
From eq.(5) & (6)
r2 – r1=(2 ln9)t≈4.4t
A plot of eq.(4) is shown below
(r )
4.4t
0 0.90
0.50
R
0.10
0 r
Figure 1.1
The charge densities of nucleons in 27Co and 83Bi nuclei versus radial distance from
centre is plotted in figure (1.2).
(r )
83 Bi
27 Co
0 r
Figure 1.2
4
From the figure (1.2), it is evident that 0 (interior value of nuclear charge
density) decreases slowly with increasing A (mass number).
The charge density (r ) corresponds the density of the protons in the nucleus and
m r represents the density of all nucleons (matter) in the nucleus. Experimental
results indicate that
Z
r r
A m
Experimental observations show that m 0 (interior value of nuclear mass
density) is approximately the same for all nuclei.
1.3Nuclear
1.3 NuclearSpin
Spin(Total
(TotalAngular
AngularMomentum)
Momentum)
Angular momentum of a nucleon can be described as:
(i) Spin Angular Momentum
Each nucleon (proton or neutron) has spin angular momentum
1 1 3
s s(s 1) 1
2 2 2
where s = 1/2 spin angular momentum quantum number.
Proton and neutron are fermions each with spin quantum number s =1/2 .
(ii) Orbital Angular Momentum
The magnitude of orbital angular momentum can be expressed as
( 1)
where l= orbital quantum number.
(iii) Total Angular Momentum
The magnitude of the total angular momentum of the nucleon is
J j(j 1)
The net angular momentum of the nucleus is the resultant of all the spin
angular momenta and orbital angular momenta of the its constituent nucleons.
The magnitude of the nuclear angular momentum due to all nucleons is
5
( 1)
where I is called total angular momentum quantum number or nuclear spin
which may be an integer or a half integer.
Greatest possible component of the total angular momentum along any direction is
I Z mI
mI= – I, – I +1, ........, I –1, I
where mI = magnetic total angular momentum quantum number.
The word spin usually refers to the resultant angular momentum of a nucleus in
nuclear physics, whereas, in atomic physics the word spin refers to the intrinsic
spin angular momentum.
It is found that nuclei with even Z and even N have the total angular momentum
zero, because pairs of protons are formed in such a way that their angular momenta
cancel and similarly pairs of neutrons are formed in such a way that their angular
momenta cancel.
The total angular momentum quantum number I is integral for nuclei with even
mass number A and half integral for nuclei with odd mass number A.
Following conclusion about total angular momentum of a nucleus can be made
Mass Proton Neutron Nuclear spin I
Number A Number Z Number N
Even Even 0
Even
Odd Odd 1,2,3,....
Even Odd 1 3 5
, , ,....
2 2 2
Odd
Odd Even 1 3 5
, , ,....
2 2 2
Shell model has been developed to find the angular momentum of a nucleus. Shell
model energy diagram is given as:
6
1g9/2 10
2p1/2 2
1f5/2 6
2 p3/2 4
1f7/2 8
1d3/2 4
2s1/2 2
6
1d5/2
1p1/2 2
1p3/2 4
1s1/2 2
Numberof
Proton States Neutron States
protonsor
neutrons
Figure 1.3
Proton and neutron states are filled separately. The filled shells have a total
angular momentum I equal to zero. Angular momentum of nucleus is determined
by the quantum state of single unpaired proton or neutron in the Shell theory. For
example, we consider a 178 O nucleus which has 8 protons and 9 neutrons.
Quantum state (see figure 1.4 ) of the last single unpaired neutron is 1d5/2 . Hence
angular momentum of the nucleus is I=5/2.
7
1d5/2
1p1/2
1p3/2
1s1/2
Proton States Neutron States
Figure 1.4 : Quantum states of 178 O nucleus in shell model
1.4
1.4Parity
Parity
The parity of a wavefunction is related to the symmetry properties of the
wavefunction .
2 2
If ( r ) ( r )
( r ) ( r )
If the spatial part of the wavefunction of a nucleus is unchanged when the space
co-ordinates (x,y,z) are substituted by (–x, –y, –z)
i.e. (–x, –y, –z) = + (x,y,z) (7)
i.e. wavefunction is invariant under reflection (function is symmetric as regards
spatial inversion) ,then system is said to have even parity.
If the spatial part of the wavefunction of a nucleus changes sign when the space co-
ordinates (x,y,z) are substituted by (–x, –y, –z) i.e.
(–x, –y, –z) = – (x,y,z) (8)
,then system is said to have odd parity i.e. function is antisymmetric as regards
spatial inversion.
The equations (7) & (8) may be combined in the form
(–x, –y, –z) = P (x,y,z)
8
( r ) P ( r )
where P 1
P= +1 corresponds to even parity (positive parity)
P= –1 corresponds to odd parity (negative parity)
For Parity operator P̂
P̂(r,t) P( r,t) with eigenvalue P = ± 1
Parity is associated with quantum number ±1 and it is also denoted by symbol π.
In spherical polar coordinates (r,,,) a reflection about the origin is equivalent to
the following transformation
rr
To a reasonably well approximation wavefunction of a nucleus is the product of
a function depending on space coordinates and a function depending on the spin
orientation. It has been found that intrinsic parity of proton as well as of neutron
is even i.e. PIntrinsic 1
Nucleon
It is found that parity of a nucleus in a given state is related to orbital quantum
number l in the following manner
P ( 1) l
The orbitals s,p,d,f,... correspond to l= 0,1,2,3,… respectively.
Parity is even for even l and parity is odd for odd l.
If r1, r2 ,...... rA are coordinates of nucleons in the nucleus and N ( r1, r2 ,...... rA ) represents
the nuclear wavefunction in a state of definite parity, then
N (r1, r2 ,.........rA ) N (r1, r2 ,........ rA )
To a good approximation, the wavefunction of the nucleus is the product of the
wavefunctions of its constituents particles. If the nuclear particles have angular
momentum quantum numbers l1 , l2 , ......respectively, then parity of the nucleus is
the product over all nucleons is given by
P=P1 P2 P3....... = i Pin (i) Pl (i)
9
= i Pl (i) { Pintrinsic 1 for nucleon}
nucleon
= (1) (1) .......... (1) ....
1 2 1 2
P (1)i
If li even then P=+1 and if li odd then P= –1
The total angular momentum is generally called the nuclear spin and it is
represented by I, but it is different from the spin angular momentum.
The parity of a nucleus is usually represented by a superscript + or – on the total
angular momentum (spin) of the nucleus.
P (spin)parity
Spin-parity state of a nucleus is completely determined by a single unpaired
proton or neutron.
For even Z - even N nuclei :
P +
I =0 (ground state)
Inner shells are completely filled. Protons and neutrons in an even N-even Z
nucleus tend to pair off separately.
For even Z-odd N nuclei or even N-odd Z nuclei:
Total angular momentum and parity are determined by the unpaired nucleon .
1
I
2
, P=(–1)l (ground state)
where l represents the orbital angular momentum quantum number of the unpaired
nucleon.
For odd Z-odd N nuclei :
Parity P ( 1) n p
Parity is important quantity in physics. Parity is conserved in strong and
electromagnetic interactions but parity is not conserved in weak interactions.
1.5
1.5Illustrative
IllustrativeExamples
Examples
Example 1 What is the parity of the following quantum state
r
a0
B r e sin e i
10
r
a
Sol. ( r ) Bre 0 sin )e i (
r
a0
Bre sin e i e i
r
a0
Bre sin e i (1)
( 1)( r )
Hence parity P= −1
Example 2 Find the angular momentum and parity of the nucleus 41Ca .
41
Sol. Quantum states of 20 Ca nucleus in shell theory are shown in figure given
below
1f7/2 8
1d3/2 4
2s1/2 2
1d5/2 6
1p1/2 2
1p3/2 4
1s1/2 2
Numberof
Proton States Neutron States
protonsor
neutrons
Figure 1.5
Nucleus 2041Ca has 20 protons and 21 neutrons. 20 protons and 20 neutrons form
closed shells whereas 21st neutron goes to quantum state 1f7/2 . The spin parity of
41
20 Ca is determined by the unpaired neutron in the state 1f7/2 . For this state
3 P 7
I =7/2 and l=3, Thus parity P= (–1) = –1 and I = 2
11
1.6
1.6Self
SelfLearning
LearningExercise-I
Exercise-I
R
Q.1 What is the nature (shape) of the graph of ln versus ln A ?
R0
Q.2 What are the eigen values of parity operator ?
Q.3 Find the electric potential energy due to electric repulsion between two
nuclei of 1327 Al when they touch each other at the surface. (Assume that
R0=1.1×10−15m)
Q.4 Find the parity of 189 F nucleus.
1.7
1.7Magnetic
MagneticMoment
Moment
The spacing in hyperfine structure indicates that the magnitude of nuclear moments
are of the order of 2e
m
where mp is the mass of the proton. The magnetic moment
p
of a nucleus is expressed in terms of the nuclear magneton µN
e J eV
N 5.05 10 27 3.15 10 8
2m p T T
e
We know that Bohr Magneton B
2me
Thus = B 1836
N
Spin Magnetic Moment:
A free proton has spin magnetic moment component in any direction (say z
direction) is given by
µ
sp z
2.793 µN
The spin magnetic moment of the proton is parallel to its spin angular
momentum.
The spin magnetic moment component of a neutron in any direction (say z
direction) is given by
µsn z – 1.913 µN
It means that spin magnetic moment of the neutron is opposite to its spin angular
momentum.
12
In order to understand the magnetic moments of a proton and a neutron (neutral
particle), internal structures of them are considered.
We can express the spin magnetic moment for proton and neutron as
e
s g s s
2m p
and s z g s N ms
where magnetic spin quantum number ms= ±1/2
gs = nuclear g factor
For proton gsp=+5.5855 (sp )z 2.793N
For neutron gsn=−3.826 (sn )z 1.913N
Orbital Magnetic Moment:
There may be orbital angular momentum due to motion of the nucleons within the
nucleus. The component of the orbital magnetic moment of a proton along the z
axis (arbitrary direction) is
e e
M Lz Lz m Nm
2mp 2mp
ml = magnetic orbital quantum number
Neutron does not have the orbital magnetic moment because it has no charge.
For proton glp =1
For Neutron gln=0
Resultant Magnetic Moment:
To a good approximation, resultant magnetic moment of a nucleus is directly
proportional to the nucleus spin I and we can write
µnucleus=µNg I
Here g is the characteristic of each nucleus.
Nucleus with zero nuclear spin (total angular momentum) has no magnetic
moment. Thus even N - even Z nuclei have no magnetic moment. Paired
nucleons do not contribute to the magnetic moment.
13
Magnetic moments of electrons and nucleus interact and this interaction splits the
atomic levels which gives rise to the hyperfine structure of the lines of the atomic
spectra.
It is found that many nuclei are in the shape of an ellipsoid instead of sphere.
Deviation of charge distribution of nucleus from a spherical shape is a measure
of nuclear electric quadrupole moment.
Quadrupole moment Q is defined as
3z
2
Q r 2 dV
where is the nuclear charge density, dV = volume element
S.I. unit of Q is C-m2
Sometimes Q is also defined as
1
Q (3 z 2 r 2 ) dV
e
where e=1.6x10-19 C and then unit of Q will be barn where 1Barn 1028 m2
If the nucleus has spherically symmetric charge distribution, then it has no
electric quadrupole moment or higher electric moments.
The charge distribution will be stretched in the z direction (prolate shape) if
quadrupole moment is positive. If quadrupole moment is negative, then charge
distribution will be in oblate shape.
z
y y
x
x
Prolate Q>0 Oblate Q 0
Figure1.6
It is observed that nuclei of both magic N and Z have zero quadrupole moments
and hence are spherical.
14
1.8
1.8Binding
BindingEnergy
Energy
Nucleus is assumed to be composed of neutrons and protons. When neutrons and
protons combine to form a nucleus, there is a loss in mass. So binding energy of
the nucleus is the energy equivalent of the missing mass of the nucleus. If m be
the missing mass of the nucleus, then binding energy Eb may be expressed as
Eb m c 2 where c 3 108 m / s
When the nucleons which are initially far away from each other are brought closer
to form the nucleus , the amount of energy released is called the binding energy of
the nucleus.
Alternatively ,we can say that the amount of energy required to separate the
constituent nucleons to large distances is called the binding energy of the nucleus.
The term missing mass m is known as mass defect. The greater value of the
binding energy of nucleus means that the more energy is needed to break the
nucleus into its constituent particles. Thus binding energy is related to stability of
the nucleus. Stable nuclei have positive value of the binding energy. Nuclear mass
is found to be always less than the sum of the masses of constituent nucleons. The
principle of equivalence of mass and energy confirms the idea of mass defect.
The binding energy of a nucleus of rest mass ZAm composed of nucleons of rest
masses mi is written as
Eb m i
A
Z m c2
i
If mass number of nucleus is A and there are Z protons and (A−Z) neutrons , then
binding energy is stated as
Eb Zm p ( A Z )mn ZA m c 2 (in Joule)
Here mp and mn are the rest masses of the proton and neutron respectively. In above
expression masses are taken in kg.
Eb Zm p ( A Z )mn ZAm 931.49 MeV (9)
Here all masses are taken in unified atomic mass unit u.
MeV
1u 931 .49
c2
15
rest mass of one neutral 126 C atom 1.99265 1026 Kg
1u
12 12
1u 1.66054 1027 Kg
Atomic mass unit (symbol : a.m.u.) was based on oxygen and it was replaced by
unified atomic mass unit (symbol: u) in 1961 to take standard same form in physics
MeV
and chemistry. Note that 1 a.m.u. can also be taken as 1amu 931.49 c2
Nuclear binding energy is of the order of MeV whereas binding energy of
electrons in atom is of the order of eV. Hence binding energy of electrons in atom
is negligible in comparison with nuclear binding energy. So without appreciable
error , binding energy of the nucleus may be approximated as
Eb ZM H ( A Z )mn ZAM atom c 2 (10)
where M H is the rest mass of the hydrogen atom.
In addition to masses of protons , the term ZM H includes the masses of Z
electrons. Similarly the term ZAM atom also contains the contribution of masses of Z
electrons. Hence ,in the above expression of the binding energy Eb contributions of
masses of electrons cancel out.
Packing Fraction:
It is defined as
Packing Fraction f M A A ,where M is the atomic mass of the neutral atom.
Above expression may be written as M A(1 f )
Packing fraction f is a function of mass number A .
Unified Atomic Mass Unit is defined for carbon as M 126C 12.0000000 u
Hence by definition, packing fraction is zero for 126C .
Variation of Binding Energy per Nucleon with Mass Number:
Average binding energy per nucleon is more useful parameter for measurement of
stability of a nucleus. It is defined as
Total binding energy of the nucleus E
Average binding energy per nucleon Eb = Total = b
number of nucleonsin the nucleus A
16
4
For example, let’s consider nucleus 2 He which has binding energy 28.3 MeV ,then
Eb 28 .3 MeV
Eb 7 .07
A 4 Nucleon
The binding energy per nucleon as a function of mass number A is plotted in
figure(1.7).
MeV/ nucleon
56
Eb 9 26 Fe 127
53 I
A 12
16
O 100 208
Pb
8 C
6
8 42 Mo 82
160
4
2 He Be 8
66 Dy
4
238
7 U
92
5 6
3 Li
4
3
2
2
1 1 H
0 4 8 12 16 20 24 30 60 90 120 150 180 210 240
Massnumber A
Figure 1.7
The binding energy per nucleon versus mass number characteristic curve has
following main features:
(i) Binding energy per nucleon is lower for both light nuclei (A≲30) and heavy
nuclei (A≳170). On the average, nuclei of intermediate masses (A≃50-80)
are the most stable.
(ii) The binding energy per nucleon is fairly constant for the nuclei of middle mass
numbers (about 30 < A < 170). In this region Eb has value about 8 MeV .
With further increase in the mass number A , the binding energy per nucleon
decreases slowly to about 7.6 MeV for A≃240. This happens due to long range
17
repulsive Coulombic force between the protons in the nucleus.
(iii) The peak at A=4 for nucleus 24 He indicates the unusual high stability of the
nucleus (alpha particle) 24 He which is made of two protons and two neutrons.
Similarly there is a also rapid rise in the value of Eb for light nuclei with
maxima for the even Z-even N nuclei such as 126C , 168O .At these nuclei Eb is
remarkably greater than those of their adjacent neighbours.
(iv) The curve has its maximum of 8 .8 MeV when the mass number is 56 that is an
iron isotope 2656 Fe which is the most stable nucleus.
(v) If a heavy nucleus of very high mass number is split into two medium mass
fragments, this process is known as fission. In the fission process, energy is
liberated because medium mass product nuclei have higher binding energy per
nucleon compared to original heavy nucleus.
MeV
For example 238
92 U (for which Eb is about 7 .6
Nucleon
) splits into two fragments
of equal masses say mass number of 119. Approximate value of Eb is
MeV
8.5
Nucleon
for nuclei having A=119. So gain in binding energy per nucleon is
MeV
8.5 7.6 0.9
Nucleon
.Hence energy released in the process is about
238 0 .9 210 MeV
(vi) In nuclear fusion , two or more nuclei of very small mass number A combine
to form a medium nucleus of higher mass number A and energy is released in
this process because product nucleus has higher average binding energy per
nucleon.
1.9
1.9Semi
SemiEmpirical
EmpiricalMass
MassFormula
Formula
Scientists developed nuclear liquid drop model to give physical insight into nuclear
properties .In this model nucleus is assumed like a liquid drop in which nucleons
are closely packed. For expressing the atomic mass ,in 1935 ,Van- Weizsacker
developed a formula which is known as semi empirical mass formula in which
certain properties of classical liquid drop is used.
From eq.(10) binding energy of the nucleus is given by
Eb ZM H ( A Z )mn ZAM atom c2
18
A E
Z M atom ZM H ( A Z ) mn 2b (11)
c
where ZA M atom is the mass of the neutral atom .
Now we discuss the various terms that contribute in the binding energy
(a) Volume Energy EV
This term is based on saturation property of nuclear forces. Nuclear forces among
nucleons are very strong and have very short range about 3fm. We can visualize
each nucleon as a sphere and these are assumed to be closely packed in which each
nucleon touches the 12 neighbouring nucleons. It can be assumed that interaction
between any two nearest neighbouring nucleons ,results in certain interaction
energy. Total interaction energy of such type depends on number of adjacent pairs
of nucleons, i.e. depends on the mass number (total number of nucleons in the
nucleus). Since volume of the nucleus is directly proportional to A ,so this type of
interaction energy is related to volume of the nucleus. Attractive nuclear forces
results in negative interaction energy but binding energy is taken as positive.
Hence binding energy corresponding to this interaction can be approximated as
Volume Binding Energy Ev av A
where av is positive constant.
(b) Surface Energy ES
Nucleons on the surface have fewer neighbours and they are not completely
surrounded .The nucleon on the surface feels attractive forces only from one side
whereas the nucleon in the interior feels attractive forces from all sides. In the
volume energy term ,it was assumed that each nucleon interacts with other
nucleons equally from all sides, so a term that is proportional to the surface area of
nucleus must be subtracted to reduce the binding energy. This negative correction
constitutes the surface energy term ES which represents the loss of binding energy.
E S R 2
E S a S A2 / 3 R R0 A1/ 3
Since lighter nuclei have greater fraction ( ratio of number of nucleons on the
surface to those in the interior volume), so surface energy term is the most
significant for lighter nuclei.
19
(c) Coulomb Energy
Coulombic repulsion force between protons is long range force. The Coulomb
potential energy (of Z protons packed together in spherical symmetric manner) is
proportional to number of proton pairs Z Z 1 and is inversely proportional to
2
nuclear radius.
The contribution to the binding energy is expressed as
Z Z 1
EC
R
Z Z 1
Ec ac
A1/ 3
The Coulombic repulsive energy term lowers the binding energy and increases the
mass , hence it opposes nuclear stability .For heavier nuclei Z 1 ,hence EC can
be approximated as
Z2
EC aC
A1/ 3
(d) Asymmetry Energy
The asymmetry energy Ea arises due to unequal number of neutrons and
protons in the nucleus. To get the best agreement with predicted binding energy
,it can be written as
2
Ea aa
N Z Here neutron excess N Z
A
2
Ea aa
A 2Z
N A Z
A
The contribution of the asymmetry energy to the binding energy is negative
because it decreases the binding energy of the nucleus .This correction term cannot
be understood with simple liquid drop model ,it is a purely quantum mechanical
effect which is related with nuclear energy levels. To be in the stable state ,nucleus
should occupy the lowest energy state. The asymmetry energy Ea is zero for Z=N
that results in greater stability of the nucleus.
(e) Pairing Energy
The nuclei having even numbers of both protons and neutrons are strongly
favoured and most stable in nature whereas nuclei having odd numbers of both
20
protons and neutrons are the least stable. Hence this pairing effect (spin
consideration) is taken in the pairing energy which can be expressed empirically as
ap
E p , 0
A3 / 4
The pairing energy is positive for even- even nuclei and zero for odd-even nuclei
or even-odd nuclei and negative for odd-odd nuclei i.e.
ap
Ep for even Z and even N
A3 / 4
Ep 0 for even Z and odd N
or odd Z and even N
ap
Ep for odd Z and odd N
A3 / 4
Here ap is assumed an approximately constant coefficient.
The total binding energy of a nucleus of atomic number Z and mass number A is
written as
Eb Ev Es Ec Ea E p
Semiempirical Binding Energy Formula
2
2/3 Z Z 1 A 2Z ap
Eb av A as A ac 1/ 3
aa , 0 (12)
A A A3 / 4
A E
From eq.(11) Atomic mass Z M atom ZM H ( A Z ) mn 2b
c
Semiempirical mass formula
2
1 Z Z 1 A 2Z a p
A
Z M atom ZM H ( A Z )mn 2 av A as A2 / 3 ac a a , 0
c A1/ 3 A A3 / 4 (13)
A set of constants av , as , ac , aa and a p have been determined as
av 14.1 MeV
as 13.0 MeV
ac 0.595 MeV
aa 19.0 MeV
a p 33.5 MeV
21
Other sets of constants have also been developed by empirically fitting the
observed mass.
Eq.(13) is known as the semiempirical mass formula because the constants
av , as , ac , aa and a p are determined empirically by fitting observed atomic masses.
The semiempirical mass formula predicts the binding energies which are
remarkably close to the observed values except those of very small A. The
discrepancies between predicted mass values and observed mass values are the
least.
1.10Illustrative
1.10 IllustrativeExamples
Examples
Example 3 Calculate the atomic mass of 49 Be .The binding energy of the nuclide
9
4 Be is 58.11628 MeV
Given that atomic mass M 11H 1.00782 u ,
Mass of neutron mn 1.00866 u and 1 u 931.5 MeV
2
c
Sol. H 5m M Be c
Eb 4 M 1
1 n
9
4
2
M 9
4 Be 4M H 5m Ec
1
1 n
b
2
58.11628 MeV
4 1.00782 u 5 1.00866 u
c2
58 .11628 u
4 1.00782 u 5 1.00866 u
931 .5
4.03128 u 5.04330 u 0.06239u
M Be 9.01219 u
9
4
17
Example 4 Calculate the binding energy of the last neutron in the nucleus 8O .
Given that atomic masses
M 178O 16.99913 u , M 168O 15.99492 u , M 11H 1.00782 u
Mass of neutron mn 1.00866 u and 1u 931.49 MeV
2
c
Sol. The binding energy of a nucleon is the energy required to remove that nucleon
from the nucleus.
Binding energy of the last neutron
22
O m M O c
Ebn M
16
8 n
17
8
2
931.49 MeV
M O m M O
16
8 n
17
8 c 2
c 2
15.99492 1.00866 16.99913 931.49 MeV
17.00358 16 .99913 931 .49 MeV
0 .00445 931.49 MeV
Ebn 4.15 MeV
1.11
1.11Self
SelfLearning
LearningExercise-II
Exercise-II
Q.1 What is the value of nuclear magneton ?
Q.2 Binding energy per nucleon is maximum for iron isotope 2656 Fe . Is this
statement true?
Q.3 Calculate the binding energy of nucleus 238 92 U .Also find the binding energy
per nucleon of the nucleus. Given that atomic masses
M 238
92U 238.05076 u , M 1 H 1.00782 u
1
Mass of neutron mn 1.00866 u and 1u 931.49 MeV
2
c
Q.4 Explain the pairing energy term in semiempirical mass formula.
1.12
1.12Summary
Summary
Nuclear radius R R0 A1/3
Nuclear mass density is of the order of 1017 kg3 .
m
Greatest possible component of total angular momentum of a nucleus along any
direction is I Z mI
mI= – I, – I +1, ........, I –1, I
where mI = magnetic total angular momentum quantum number.
For Parity operator P̂ we have P̂(r,t) ≡ P( r,t) with eigen value P = ± 1
It is found that parity of nucleus in a given state is related to orbital quantum
number l in the following manner P (1)l
Quadrupole moment Q is defined as
23
3z
2
Q r 2 dV
where is the nuclear charge density, dV = volume element, S.I. unit of Q is
C-m2
Sometimes Q is also defined as Q 1e (3 z2 r 2 ) dV
If the nucleus has spherically symmetric charge distribution, then it has no
electric quadrupole moment or higher electric moments.
Binding energy of the nucleus Eb Zm p ( A Z )mn ZAm 931.49 MeV
Here all masses are taken in u where 1u 931.49 MeV
2
c
Eb ZM H ( A Z )mn ZAM atom c2
The curve plotted binding energy per nucleon versus mass number has its
maximum of 8 .8 MeV when the mass number is 56 that is an iron isotope 2656 Fe
which is the most stable nucleus.
Semiempirical binding energy formula
2/3 Z Z 1 A 2 Z 2 ap
Eb av A as A ac 1/ 3
aa , 0
A A A3 / 4
1.13Glossary
1.13 Glossary
Nucleon : protons and neutrons
Even -even nuclei: nuclei having even Z and even N
Parity: The parity of a wave function is related to the symmetry properties of
the wavefunction . Parity operator P̂ we have P̂(r,t) ≡ P( r,t) with eigen
value P = ± 1
1.14
1.14Answers
AnswerstotoSelf
SelfLearning
LearningExercises
Exercises
Answers to Self Learning Exercise-I
Ans.1: Straight line ln RR 31 ln A with slope 31 .
0
Ans.2: 1
Ans.3: Nuclear radius R= R0A1/3=1.1× 10−15 (27)1/3
24
= 3.3 × 10–15m
q1q2
Mutual electric potential energy U 41 R
9 19 19
9 x10 (13 x1.6x10 )(13 x1.6 x10 )
U
3.3 x10 15
6 –19
=73.75 ×10 ×1.6×10 Joule
=73.75 MeV
Ans.4: According to shell model 9th proton and 9th neutron are unpaired and each
lies in the respective states 1d5/2
Hence ln=2 and lp=2
l lp
P ( 1) n 1
Answers to Self Learning Exercise-II
e J eV
Ans.1: N 5.05 10 27 3.15 108
2m p T T
Ans.2: True
Ans.3: Binding energy
Eb ZM H ( A Z )mn ZAM atom c2
Eb 92M H 146m M
1
1 n
238
92U c 2
92 1.00782 u 146 1.00866 u 238.05076 u c2
1.93304 uc2
1.93304 931.49 MeV
1800.61MeV
Binding energy per nucleon EAb 1800.61
238
MeV
Nucleon
7.57
MeV
Nucleon
1.15
1.15Exercise
Exercise
Q.1 What is the value of the electric quadrupole moment of nucleus which has
spherically symmetric charge distribution ?
Q.2 What is the order of nuclear mass density ?
Q.3 Magnetic moments of electrons and nucleus interact and this interaction
25
splits the atomic levels which gives rise to the…………….(fine/hyperfine)
structure of the lines of the atomic spectra.
Q.4 What is the value of 1 Barn ?
Q.5 Define mass defect and packing fraction.
Q.6 Explain the asymmetry energy term in semiempirical mass formula.
Q.7 Compare the nuclear density of 11H with its atomic density (Assume the
atomic radius is equal to the first Bohr orbit).
Q.8 Write the main features of curve of binding energy per nucleon versus mass
number.
Q.9 Find the spin-parity of the following nuclei
(i) 3919 K (ii) 178 O (iii) 157 N
Q.10 Describe the semiempirical mass formula for the nucleus.
1.16
1.16Answers
AnswerstotoExercise
Exercise
Ans.1: Zero.
Ans.2: Nuclear mass density is of the order of 1017 kg3 .
m
Ans.3: hyperfine structure
Ans.4: 1Barn 1028 m2
Ans.7: Over 1014 times
Ans.9: (i)
1s1/2 1p3/2 1p1/2 1d5/2 2s1/2 1d3/2
Protons 2 4 2 6 2 3=2+1
Neutrons 2 4 2 6 2 4
Quantum state 1d3/2 i.e. 3/2+
(ii) Quantum state 1d5/2 i.e. 5/2+
(iii) Quantum State 1p1/2 i.e. 1/2−
26
References
Referencesand
andSuggested
SuggestedReadings
Readings
1. Herald A. Enge, Introduction to Nuclear Physics (1966), Addison Wesley
Publishing Company.
2. Bernard L. Cohen, Concepts of Nuclear Physics (2002), Tata McGraw-Hill.
3. Irving Kaplan, Nuclear Physics (Second Edition 2002), Narosa Publishing
House.
4. R.R. Roy & B.P. Nigam, Nuclear Physics (2000), New Age International (P)
Ltd.
5. Kenneth S. Krane, Introductory Nuclear Physics (2008), Wiley India Pvt. Ltd.
6. Robert Eisberg & Robert Resnick, Quantum Physics of Atoms, Molecules,
Solids, Nuclei and Particles ( 2006) ,John Wiley & Sons (Asia) Pte. Ltd.
7. Arthur Beiser, Shobhit Mahajan & S.Rai Choudhury, Concepts of Modern
Physics (Seventh Edition 2015), McGraw-Hill.
8. D.C.Tayal, Nuclear Physics (Fourth Edition 2001), Himalaya Publishing
House.
9. Robert D. Evans, The Atomic Nucleus (1955), McGraw-Hill Book Company
,Inc.
10. J.B. Rajam ,Atomic Physics (Seventh Edition 2002), S. Chand & Company
Ltd.
11. Young & Freedman, University Physics, (Eleventh Edition 2004), Pearson
Education, Inc.
12. David Halliday, Robert Resnick & Kenneth S. Krane, Physics Volume -II
(Fifth Edition 2004 ) ,John Wiley & Sons (Asia) Pte. Ltd.
13. Marcelo Alonso & Edward J. Finn, Physics (1999), Addition Wesley
Longman , Inc.
27
UNIT-1
UNIT-2
Two Nucleon System and Forces
Structure of the Unit
2.0 Objectives
2.1 Introduction
2.2 General nature of the force between nucleons
2.3 Self learning exercise-I
2.4 General form of two nucleon interaction
2.5 Properties of nuclear force
2.6 Self learning exercise-II
2.7 Summary
2.8 Glossary
2.9 Answers to self learning exercises
2.10 Exercise
References and Suggested Readings
2.0
2.0Objectives
Objectives
After interacting with the material presented here students will be able to
understand
general nature of nuclear force
properties of nuclear force and
the general form of nuclear potential.
2.1
2.1Introduction
Introduction
At the beginning of the twentieth century, the science of physics knew about three
basic forces: gravitational, electric, and magnetic. All forces, whether they were
"action at a distance" or field forces, could be always interpreted as one these three
28
forces and it was believed that all other forces like elastic forces, collision forces,
etc could be understood in terms of these three forces.
By the end of first quarter of the twentieth century a fourth force was found. With
electrostatic, magnetic, and gravitational forces, measurement could be made in the
laboratory or on a macroscopic scale and the laws governing these forces were
established. But entirely new methods were required to study the nuclear binding
forces; by the 1960's the form of the laws governing these forces had not been
established on a firm basis.
2.2
2.2General
GeneralNature
Natureofofthe
theForce
Forcebetween
betweenNucleons
Nucleons
We can enumerate the following properties of nuclear force on the basis of various
observations and empirical facts:
1. Nuclear force is always attractive between two neutrons, or two protons or
neutron and proton. Existence of neutrons and protons in a bound state is itself an
evidence of this.
2. Nuclear force is short ranged. If it were not so, all the nucleons in different
nuclei will coalesce into one big nucleus and everything will probably turn into a
huge nucleus like a super-neutron star, and there will be no more a variety of
elements in nature.
3. Nuclear force is very strong. This is evident from the large binding energy of
nuclei (about 8 MeV per nucleon). The average binding energy of electrons in
atoms is in the range of eV to keV only.
4. Nuclear force saturates. This is actually an outcome of the short range nature
of the nuclear force. Each nucleon in a nucleus interacts with its neighbors only.
As a result the binding energy per nucleon rises rapidly for light mass nuclei and
quickly saturates
Figure shows the measurements of the energy needed to strip out a nucleon from a
nucleus as a function of the number of nucleons in the nucleus, i.e. the binding
energy per nucleon, rises rapidly up to A~10-20 and then levels off at
approximately 7.5 MeV/nucleon.
If we assume that a nucleon interacts with all the other nucleons in the nucleus then
there should be A(A-1)/2 pairs of nuclei. Since the binding energy increases with
29
the number of interactions BE ~ A(A-1)/2. Then BE/A would be linear, which it is
but only roughly up to around A~10.
The binding energy curve suggests that nucleons only interact with their nearest
neighbours. The range of the force must be less than the size of a mass-10 nucleus,
which is around 1.2x101/3= 2.6 fm. This property is described as saturation of the
nuclear force.
5. Nuclear force is charge symmetric. It is same for a p-p and an n-n pair
(ignoring the Coulomb repulsion between p-p). As an example consider the
following evidence for charge symmetry.
30
3 3
H He
Z=1, N=2 Z=2, N=1
2 p-n pairs and 1 n-n pair 2 p-n pair and 1 p-p pair
BE=8.48MeV BE=7.71MeV
The difference in the BE between the two is 0.77 MeV. 23 He1 assuming to be a
uniformly charged sphere of radius 2.24 Fermi, the difference is almost entirely
accounted for by Coulomb energy implying that p-p and n-n interaction is same.
6. Nuclear force is charge independent. The force is same for n-p as it is for n-n
and p-p pairs provided the n-p pair is in the same isospin state (T=1). A p-p and an
n-n pair can occupy isospin T=1 state only. If the n-p pair also occupies T=1 state
then the force is the same.
One cannot say from mirror nuclei anything about n-n and p-p forces compared to
n-p forces. But if we gradually change the individual nucleon types, one by one,
into the other we generate a series of nuclei with the same mass, but a range
different numbers of protons and neutrons. To make a fair comparison for the
strong interactions, we can again correct for the Coulomb effects and the difference
in the proton and neutron masses.
For example, the 0+ ground states of 30Si and 30S , and an excited 0 state in 30P
are at a very similar mass-energy. The 2 states of 30Si and 30S also have an
isobaric analogue in 30P, as do other levels. Transition probabilities and reaction
rates based on strong interactions involving these states also show similarities.
Consider the changes in going from 30Si and 30P . A neutron turns into a proton.
We already know that the n-n and p-p forces are similar. So the experimental
similarity of the 30Si level scheme with a subset of states in the 30P level scheme
must imply that the n-p force must also be of similar strength. Nuclear forces
display charge independence.
31
7. Nuclear force is spin dependent. As an example, deuteron in its ground state
(and the only bound state) exists only in spin triplet state. The spin singlet state is
unbound. This property will be further discussed in chapter 3.
8. Nuclear force has a tensor nature. The arrangement of nucleon spins in a
nucleus – whether two nucleons are placed side by side or, one on top of the other
although total spin is 1 in both the cases - makes a difference in their binding
howsoever small.
The tensor dependence is generally expressed by the term,
1 2
S12 [3( 1 . r )( 2 . r ) ( 1 . 2 ) r ]
r2
If 1 and 2 are parallel to r and if the two are perpendicular to r, the value of
(1. 2) is different in the two cases even for the same value of the total spin
i.e. . The magnetic moment of deuteron cannot be explained without the tensor
nature of nuclear force.
9. Nuclear force also has velocity dependence or, a dependence on the spin-orbit
term. It is given be a term like
1
V12 L( 1 2 )VLS ( r )
2
It is attractive when L and S (=1/2(1+2)) are parallel and repulsive when they
are anti-parallel.
10. Nuclear force has an exchange character. This is a purely quantum feature
and may be understood by knowing the way nuclear force is mediated. Two
nucleons, when interacting with each other, can exchange their spin, isospin, or a
combination of both. These are represented by Bartlett (B), Heisenberg (H), and
Majorana (M) terms which contribute to the force according to the signs given
below:
Even l, +ve parity Odd l, -ve parity
s=1 s=0 s=1 s=0
W +1 +1 +1 +1
32
B +1 -1 +1 -1
M +1 +1 -1 -1
H +1 -1 -1 +1
The sign depends on the nature of state (the l-value, s-value and the parity). W
represents the Wigner term which is no exchange at all. Bartlett force leads to spin
exchange, Majorana force to isospin exchange and Heisenberg force to a
combination of spin and isospin.
2.3
2.3Self
SelfLearning
LearningExercise-I
Exercise-I
Q.1 Explain the evidence for attractive nature of nuclear forces.
Q.2 Draw binding energy per nucleon graph.
Q.3 Write down the term which represent the tensor dependence of nuclear
force.
Q.4 Define the exchange character of nuclear force.
Q.5 Write down the properties of nuclear forces.
2.4
2.4General
GeneralForm
FormofofTwo
TwoNucleon
NucleonInteraction
Interaction
The interaction of two nucleons at low energy can be described by a potential of
the form
V ( r ) Vcent ( r ) VSS ( r ) s1 .s2 VT ( r )[3( s1 .r )( s2 .r ) / r 2 s1s2 ]
+VLS ( r )( s1 s2 ).L VLS ( r )( s1 .L )( s2 .L ) VPS ( r )( s1. p )( s2 . p )
Where
r denotes the relative distance of the nucleons with spins s1 and s2,
p is the relative momentum and
L is the total orbital angular momentum.
The potential neglects the inner structure of the nucleons and is therefore valid
only for bound states and for low-energy NN scattering, from which its form can
be derived. Interpretation of the different terms:
33
1. Central potential.
2. Central spin-spin interaction.
3. Tensor (non-central) potential. It has the same spin dependence as the
magnetic interaction of two magnetic moments. This term is the only one
which may lead to a mixing of different orbital angular momentum in the
physical state.
4. LS coupling, similar to atomic physics, but caused by the strong force.
5. and 6 terms respect basic symmetries but may often be neglected due their
quadratic dependence on p.
To describe nuclei, additional many-body forces have to be taken into account,
leading to a still higher level of sophistication.
2.5
2.5Properties
PropertiesofofNuclear
NuclearForce
Force
In this section we summarize the main features of the inter nucleon force.
Interaction between nucleons consists to lowest order of an attractive central
potential
In most of nuclear calculation we use a square-well form of potential, which
simplifies the calculations and reproduces the observed data fairly well. Other
more realistic forms could just as well have been chosen but the essential
conclusions would not change (in fact, the effective rang approximation is virtually
independent of the shape assumed for the potential). The common characteristic of
these potentials is that they depend only on the inter nucleon distance r. We
therefore represent this central term as Vc(r). The experimental program to study
VC(r) would be to measure the energy dependence of nucleon-nucleon parameters
such as scattering phase shifts, and then to try to choose the form for VC(r) that best
reproduces those parameters.
The Nucleon - Nucleon interaction is strongly spin dependent
This observation follows from the failure to observe a singlet bound state of the
deuteron .and also from the measured differences between the singlet and triplet
cross sections (discussed in Chapter 3). What is the form of an additional term that
must be added to the potential to account for this effect? Obviously the term must
depend on the spins of the two nucleons, s1 and s2 but not all possible combinations
34
of s1 and s2 are permitted. The nuclear force must satisfy certain symmetries, which
restrict the possible forms that the potential could have. Examples of these
symmetries are parity (r ~ -r) and time reversal (t ~ - t). Experiments indicate that,
to a high degree of precision (one part in 107 for parity and one part in 103 for time
reversal), the inter nucleon potential is invariant with respect to these operations.
Under the parity operator, which involves spatial reflection, angular momentum
vectors are unchanged. This statement may seem somewhat surprising, because
upon inverting a coordinate system we would naturally expect all vectors defined
in that coordinate system to invert. However, angular momentum is not a true or
polar vector; it is a pseudo or axial vector that does not invert when r ~ - r. This
follows directly from the definition r X p or can be inferred from a diagram of a
spinning object. Under the time-reversal operation, all motions (including linear
and angular momentum) are reversed. Thus terms such as s1 or s2 or a linear
combination As1 + Bs2 in the potential would violate time-reversal invariance and
cannot be part of the nuclear potential; terms such as s12 , s22 or s1.s2 are invariant
with respect to time reversal and are therefore allowed. (All of these terms are also
invariant with respect to parity.) The simplest term involving both nucleon spins is
s1.s2. Let's consider the value of s1.s2 for singlet and triplet states. To do this we
evaluate the total spin S = s1 + s2
S 2 S .S ( s1 s2 ).( s1 s2 )
=s12 s22 2 s1. s2
Thus
1
s1 .s2 = ( S 2 s12 s22 )
2
To evaluate this expression, we must remember that in quantum mechanics all
squared angular momenta evaluate as
s 2 =2 s( s 1)
1
s1 .s2 [ S ( S 1) s1 ( s1 1) s2 ( s2 1)] 2
2
With nucleon spins s1 and s2 of 1/2, the value of s1.s2 is, for triplet (S = 1) states:
1 1 1 1 1 2
s1 .s2 [1(1 1) ( 1) ( 1)]
2
2 2 2 2 2 4
35
and for singlet (S = 0) states:
1 1 1 1 1 3 2
s1 .s2 [0(0 1) ( 1) ( 1)]
2
2 2 2 2 2 4
Thus a spin-dependent expression of the form s1.s2Vs(r) can be included in the
potential and will have the effect of giving different calculated cross sections for
singlet and triplet states. The magnitude of Vs can be adjusted to give the correct
differences between the singlet and triplet cross sections and the radial dependence
can be adjusted to give the proper dependence on energy.
We could also write the potential including Vc and Vs as
s .s 1 s .s 3
V ( r ) 1 2 2 V1 ( r ) 1 2 2 V3 ( r )
4 4
where V1(r) and V3(r) are potentials that separately give the proper singlet and
triplet behaviors.
The inter Nucleon potential includes a noncentral term, known as a tensor
potential
Evidence for the tensor force comes primarily from the observed quadrupole
moment of the ground state of the deuteron (Chapter 3). An s-state (l = 0) wave
function is spherically symmetric; the electric quadrupole moment vanishes. Wave
functions with mixed l states must result from noncentral potentials. This tensor
force must be of the form V(r), instead of V(r). For a single nucleon, the choice of
a certain direction in space is obviously arbitrary; nucleons do not distinguish north
from south or east from west. The only reference direction for a nucleon is its spin,
and thus only terms of the form s • r or s X r, which relate r to the direction of s,
can contribute. To satisfy the requirements of parity invariance, there must be an
even number of factors of r, and so for two nucleons the potential must depend on
terms such as (s1 • r)(s2 • r) or (s1 X r) • (s2 X r). Using vector identities we can
show that the second form can be written in terms of the first and the additional
term s1 • s2, which we already included in V(r). Thus without loss of generality we
can choose the tensor contribution to the inter nucleon potential to be of the form
VT(r)s12, where VT(r) gives the force the proper radial dependence and magnitude,
and
S12 3( s1 .r )( s2 .r ) / r 2 s1.s2
36
which gives the force its proper tensor character and also averages to zero over all
angles.
The Nucleon - Nucleon force is charge symmetric
This means that the proton-proton interaction is identical to the neutron-neutron
interaction, after we correct for the Coulomb force in the proton-proton system.
Here "charge" refers to the character of the nucleon (proton or neutron) and not to
electric charge. Evidence in support of this assertion comes from the equality of
the pp and nn scattering lengths and effective ranges. Of course, the pp parameters
must first be corrected for the Coulomb interaction. When this is done, the
resulting singlet pp parameters are
a = -17.1 ± 0.2 fm
r0 = 2.84 ± 0.03 fm
These are in very good agreement with the measured nn parameters (a = -16.6 ±
0.5 fm, r0 = 2.66 ± 0.15 fm), which strongly supports the notion of charge
symmetry.
The Nucleon - Nucleon Force Is Nearly Charge Independent
This means that (in analogous spin states) the three nuclear forces nn, pp, and pn
are identical, again correcting for the p'p Coulomb force. Charge independence is
thus a stronger requirement than charge symmetry. Here the evidence is not so
conclusive; in fact, the singlet np scattering length (- 23.7 fm) seems to differ
substantially from the pp and nn scattering lengths (-17 fm).
37
However, we see from figure that large negative scattering lengths are
extraordinarily sensitive to the nuclear wave function near r = R, and a very small
change in ; can give a large change in the scattering length. Thus the large
difference between the scattering lengths may correspond to a very small
difference (of order 1 %) between the potentials, which is easily explained by the
exchange force model.
The Nucleon - Nucleon interaction becomes repulsive at short distances
This conclusion follows from qualitative considerations of the nuclear density: as
add more nucleons the nucleus grows in such a way that its central density remains
roughly constant, and thus something is keeping the nucleons from crowding too
closely together. More quantitatively, we can study nucleon-nucleon scattering at
higher energies. Figure shows the deduced singlet s-wave phase shifts for nucleon-
nucleon scattering up to 500 MeV. (At these energies, phase shifts from higher
partial waves, p and d for example, also contribute to the cross sections. The s-
wave phase shifts can be easily extracted from the differential scattering
measurements of d/d vs ( because they do not depend on .) At about 300
MeV, the s-wave phase shift becomes negative, corresponding to a change from an
attractive to a repulsive force. To account for the repulsive core, we must modify
38
the potentials we use in our calculations. For example, again choosing a square-
well form to simplify the calculation, we might try
V( r) = + r < R core
= − V0 (R) Rcore r R
=0 r>R
and we can adjust R core until we get satisfactory agreement with the observed s-
wave phase shifts. The value Rcore 0.5 fm gives agreement with the observed
phase shifts.
The Nucleon - Nucleon interaction may also depend on the relative velocity or
momentum of the nucleons
Forces depending on velocity or momentum cannot be represented by a scalar
potential, but we can include these forces in a reasonable manner by introducing
terms linear in p, quadratic in p, and so on, with each term including a
characteristic V(r). Under the parity operation, p - p, and also under time
reversal p - p. Thus any term simply linear in p is unacceptable because it
violates both parity and time-reversal invariance. Terms of the form r.p or r X p
are invariant with respect to parity, but still violate time reversal. A possible
structure for this term that is first order in p and invariant with respect to both
parity and time reversal is V(r)(r X p) • S, where S = s1 + s2 is the total spin of the
two nucleons. The relative angular momentum of the nucleons is l = r X p, and
therefore this term, known as the spin-orbit term in analogy with atomic physics, is
written Vso(r)l.S. Although higher-order terms may be present, this is the only first-
order term in p that satisfies the symmetries of both parity and time reversal.
The experimental evidence in support of the spin-orbit interaction comes from the
observation that scattered nucleons can have their spins aligned, or polarized, in
certain directions. The polarization of the nucleons in a beam (or in a target) is
defined as
N ( ) N ( )
P
N () N ()
where N() and N() refer to the number of nucleons with their spins pointed up
39
and down, respectively. Values of P range from + 1, for a 100% spin-up polarized
beam, to -1, for a 100% spin-down polarized beam. An unpolarized beam, with
P = 0, has equal numbers of nucleons with spins pointing up and down.
Consider the scattering experiment shown in figure, in which an unpolarized beam
(shown as a mixture of spin-up and spin-down nucleons) is incident on a spin-up
target nucleon. Let's suppose the nucleon-nucleon interaction causes the incident
spin-up nucleons to be scattered to the left at angle and the incident spin-down
nucleons to be scattered to the right at angle -. Part b of the figure shows the
same experiment viewed from below or else rotated 180 about the direction of the
incident beam. We can also interpret figure b as the scattering of an unpolarized
beam from a spin-down target nucleon, and once again the spin-up incident
nucleons scatter to the left and the spin-down nucleons scatter to the right. The
results would be the same, even in an unpolarized target, which would contain a
mixture of spin-up and spin-down nucleons: when an unpolarized beam is scattered
from an unpolarized target, the spin-up scattered nucleons appear preferentially at
and the spin-down scattered nucleons at - .
40
Although this situation may appear superficially to violate reflection symmetry
(parity), you can convince yourself that this is not so by sketching the experiment
and its mirror image. Parity is conserved if at angle we observe a net polarization
P, while at angle - we observe a net polarization of -P.
Now let’s see how the spin-orbit interaction can give rise to this type of scattering
with polarization.
Figure shows two nucleons with spin up incident on a spin up target, so that S = 1.
(Scattering that includes .only s waves must be spherically symmetric, and
therefore there can be no polarizations. The p-wave (t= 1) scattering of identical
nucleons has an anti symmetric spatial wave function and therefore a symmetric
spin wave function.) Let's assume that Vso(r) is negative. For incident nucleon 1, l=
r X p is down, and therefore l· S is negative because l and S point in opposite
directions. The combination Vso(r)l· S is positive and so there is a repulsive force
between the target and incident nucleon 1, which is pushed to the left. For nucleon
2, l points up, l· S is positive, and the interaction is attractive; incident nucleon 2 is
pulled toward the target and also appears on the left side. Spin-up incident
nucleons are therefore preferentially scattered to the left and (by a similar
argument) spin-down nucleons to the right. Thus the spin-orbit force can produce
polarized scattered beams when unpolarized particles are incident on a target.
At low energy, where s-wave scattering dominates, we expect no polarization. As
the incident energy increases, the contribution of p-wave scattering increases and
there should be a corresponding increase in the polarization. The general topic of
41
polarization in nuclear reactions is far more complicated than we have indicated in
this brief discussion.
Figure shows some representative nucleon-nucleon potentials.
2.6
2.6Self
SelfLearning
LearningExercise-II
Exercise-II
Q.1 What is polarization?
Q.2 Write down the evidence for the tensor force.
Q.3 Explain that the Nucleon - Nucleon interaction is strongly spin dependent.
42
Q.4 Write down and explain the general form of two nucleon interaction
2.7Summary
2.7 Summary
In this chapter we have discussed general nature of nuclear force. We have also
discussed various properties of nuclear forces with their evidences. This chapter
also gave a brief idea of the general form of two nucleon interaction which
includes central, noncentral and velocity dependent potentials terms.
2.8
2.8Glossary
Glossary
Spin: Spin is a characteristic property of elementary particles
Isospin: Particles appear to arrange themselves in sets of particles of different
electric charge, but nearly the same mass. They are individually labeled with a
quantum number of -1, 0, 1, or other multiples of these. Hadrons have Isospin.
Leptons have a similar arrangement and are labeled with “weak isospin” according
to their roles in the Standard Model. This is not the same as generic “isospin.”
Nuclear force: The force that holds the nucleus together. Originally thought to be
the exchange of pions, as suggested by Yukawa. Pions are now known to not be
elementary themselves, but quarks which are held together by gluons.
Nucleon: The generic name for neutrons and protons, reflecting the fact that their
Strong Interactions are identical.
Quantum Number: Quantum mechanics is full of integers which describe certain
quantum states. In atoms, these quantum numbers come from the solutions to the
Schroedinger equation, in which the principle quantum number, n, is identical to
the original idea of Bohr’s that electron orbits are fixed in radius and energy. There
are quantum numbers for angular momentum, spin, and other characteristics.
Transitions among states follow “selection rules” that relate the before and after
values of the quantum numbers of the atomic states. In elementary particle physics
Quantum Numbers appear to be inherent to particular particles and are “additive”
meaning that in many cases they are conserved…that the sum before an interaction
or decay must equal the same ones after the interaction or decay. This is especially
true in the Strong Interactions, but also in the Weak Interactions. Examples of
inherent quantum numbers are: Baryon Number, Lepton Number, Electric Charge,
Isospin, and Strangeness.
43
Polarization: The polarization of a wave is the direction in which it is oscillating.
The simplest type of polarization is linear, transverse polarization. Linear means
that the wave oscillation is confined along a single axis, and transverse means that
the wave is oscillating in a direction perpendicular to its direction of travel. Laser
light is most commonly a wave with linear, transverse polarization. If the laser
beam travels along the x-axis, its electric field will oscillate either in the y-
direction or in the z-direction. Gravitational waves also have transverse
polarization, but have a more complicated oscillation pattern than laser light.
2.9
2.9Answers
AnswerstotoSelf
SelfLearning
LearningExercise
Exercise
Answers to Self Learning Exercise-I
Ans.1: Existence of neutrons and protons in a bound state is the evidence for
attractive nature of nuclear forces.
Ans.2: See Section 2.2
1 2
Ans.3: S12 [3( 1 . r )( 2 . r ) ( 1 . 2 ) r ]
r2
Ans.4: See Section 2.2
Ans.5: See Section 2.2
Answers to Self Learning Exercise-II
Ans.1: See Glossary
Ans.2: The evidence for the tensor force comes primarily from the observed
quadrupole moment of the ground state of the deuteron
Ans.3: Section 2.5
Ans.4: Section 2.4
2.10
2.10Exercise
Exercise
Q.1 Justify the existence of tensor forces in the nucleus.
Q.2 What are the properties of nuclear forces?
Q.3 Write a short note on
a. Spin dependence of nuclear force
44
b. Charge symmetry of nuclear force
c. Charge independence of nuclear force
d. Saturation property of nuclear force
Referencesand
References andSuggested
SuggestedReadings
Readings
1. Theoretical Nuclear Physics by J.M. Bhatt and V.E. Weisskipf.
2. Nuclear Physics by B.K. Agarwal 1989.
3. Nuclear Physics by R.R. Roy and B.P. Nigam, 1979.
4. Concept of Nuclear Physics by B.L. Cohen, 1988.
5. Nuclear Physics by I. Kaplan, 1963.
6. Nuclear Physics by D. C Tayal.
7. Introductory Nuclear Physics by Kenneth S. Krane.
45
UNIT-3
The Deuteron
Structure of the Unit
3.0 Objectives
3.1 Introduction
3.2 Analysis of the ground state (3S1) of deuteron using a square well potential
3.3 Self learning exercise-I
3.4 Excited states of deuteron
3.5 Deuteron structure
3.6 Magnetic moment
3.7 Quadrupole moment
3.8 Self learning exercise-II
3.9 Answers to self learning exercises
3.10 Exercise
3.11 Summary
3.12 Glossary
References and Suggested Readings
3.0
3.0Objectives
Objectives
The main aim of this chapter is to study the Basic properties of deuteron viz, its
binding energy, its size, spin, magnetic and quadrupole moments etc. After going
through this chapter you should be able to:
Understand the various properties of deuteron.
Analyze the existence of ground and excited states of deuteron.
3.1
3.1Introduction
Introduction
In the previous chapter we have discussed various properties of nuclear force and
46
potential. The actual properties of the nuclear potential are quite complicated. We
can find out about the potential in two main ways. One is scattering of nucleons of
each other or from nuclei. The other is to study any stable states that might result
from this interaction. There are of course 3 possibilities: pn, pp, nn. It turns out that
only one of these forms a stable nucleus. We will discuss why, and what this
means. In this instance we will study the nucleus 2H, the deuteron, which is the
nucleus formed when a proton and neutron combine. It is the simplest nucleus and
in a sense is the nuclear equivalent of the H atom in atomic studies. Unfortunately,
unlike the H atom, it does not have any excited states, so there is no information
available from its spectroscopy. None the less the fact that it is bound at all reveals
a lot about the nuclear force. (of course if it were not bound, we wouldn’t be here
to study nuclear physics, since this nucleus is the basis for fusion to all the heavier
nuclei in the universe)
Some Facts about the deuteron
1. A deuteron (2H nucleus) consists of a neutron and a proton.
2. It is the simplest bound state of nucleons and therefore gives us an ideal
system for studying the nucleon-nucleon interaction.
3. An interesting feature of the deuteron is that it does not have excited states
because it is a weakly bound system
4. In analogy with the ground state of the hydrogen atom, it is reasonable to
assume that the ground state of the deuteron also has zero orbital angular
momentum L = 0
5. However the total angular momentum is measured to be J = 1 (one unit of
h/2π) thus it follows that the proton and neutron spins are parallel
sn+sp = 1/2 + 1/2 = 1
6. The implication is that two nucleons are not bound together if their spins are
anti-parallel, and this explains why there are no proton-proton or neutron-
neutron bound states.
7. The parallel spin state is forbidden by the Pauli exclusion principle in the case
of identical particles
8. The nuclear force is thus seen to be spin dependent.
47
3.2 Analysis of
3.2 Analysis of the
the Ground
Ground State (3S11)) ofofDeuteron
State (3S Deuteronusing
usingaa
Square Well
Square Well Potential
Potential
The deuteron is the simplest system of bound nucleons. Its ground state is the only
known bound state of two nucleons:
— There are no bound states between two protons, respectively, two neutrons.
— Excited states of the deuteron are unbound.
Hence, the single bound state of nucleons offer us only very restricted possibilities
to study NN interactions. Nonetheless, the ground state properties of the deuteron
already tell us some important features of the binding force.
Properties of the deuteron:
Mass: 1.876 139 MeV, determined by mass spectroscopy using penning trap
techniques
Binding energy: 2.225 MeV (i.e. ∼ 1.1 MeV per nucleon), determined from
measurement of the gamma energy in radiative capture, n (p, ) d. Compared to
typical binding energies per nucleon of heavier nuclei (∼ 8 MeV), the deuteron is
a weakly bound nuclear system. The binding is so weak that there are no excited
bound states.
Spin: J = 1, deduced from observed number of hyperfine components.
Magnetic moment: µd = 0.857 393 µN, measured via nuclear magnetic resonance.
The value is close to the sum of the magnetic moments of the free proton and the
free neutron,
µp + µn = 2.792 µN − 1.913 µN = 0.879 µN
This implies that the deuteron is essentially a state, where the two spins 1/2 of the
nucleons are parallel and add to J = 1 (remember the opposite signs of the proton
and neutron magnetic moments). This corresponds to an S state (no orbital angular
momentum).
Electric quadrupole moment: Qd = 2.86 × 10−27 cm2, deduced from the magnetic
field dependence of hyperfine lines of deuterium. The reason for the deuteron
being not spherically symmetric is a non-central part in the NN force, the so-called
tensor force. It admixes a state with orbital angular momentum to the ground state,
48
meaning that the deuteron is not a pure S state. Since the strong force conserves
parity (remember that the orbital angular momentum of a state influences its parity
by a factor (−1)l), the admixture must be a state with l = 2 (i.e. a D state), in order
to have the same quantum numbers JP .
— The sizes of both the magnetic moment and the quadrupole moment can be
derived from a wavefunction
|d >= 0.98 |3S1> + 0.20 |3D1>
where the deuteron is found with 4 % probability in the state 3D1.
To simplify the analysis of the deuteron, we assume that the nucleon-nucleon
potential is a three-dimensional square well, as shown in the figure:
Figure1
V ( r ) V0 for r < R
V (r ) 0 for r > R
In figure 2 ,here r represents the separation between the proton and the neutron, so
R is in effect a measure of the diameter of the deuteron.
The dynamical behavior of a nucleon must be described by the Schrödinger’s
equation
2 2
(r ) V (r )( r ) E ( r )
2m
49
where m is the nucleon mass.
Figure 2
If the potential is not orientationally dependent, a central potential, then the wave
function solution can be separated into radial and angular parts:
(r ) R( r )Yl m ( , )
Substitute R(r) = u(r)/r in to the Schrödinger’s equation the function u(r) satisfies
the following equation;
2 d 2 u l (l 1)2
V ( r ) u( r ) Eu( r )
2m dr 2 2mr 2
The solution u(r) is labeled by two quantum numbers n and l so that:
u( r ) unl ( r )
The full solution (r) then can be written as
( r ) nlm ( r, , ) Rnl ( r )Ylm ( , )
with
u nl ( r )
R nl ( r )
r
50
Where
n: the principal quantum number which determines
the energy of an eigenstate.
l: the orbital angular momentum quantum number.
m: the magnetic quantum number, –l ≦ m ≦ l.
The angular part of the solution Ylm(θ,) is called the “spherical harmonic” of
order l, m and satisfies the following equations:
Lˆ2Ylm ( , ) l (l 1) 2Ylm ( , )
and LˆZ Ylm ( , ) mYlm ( , )
1 1 2
where Lˆ2 2 sin 2
sin sin 2
and LˆZ i
For the case of a three dimensional square well potential with zero angular
momentum (l = 0), which we use as the model potential for studying the ground
state of the deuteron, the Schrödinger’s equation can be simplified into:
2 d 2u
V0u ( r ) Eu ( r ) for r<R
2m dr 2
2 d 2u
Eu ( r ) for r>R
2m dr 2
I. When r < R
The Schrödinger’s equation is
2 d 2u
V0u ( r ) Eu ( r )
2 m dr 2
This equation can be rearranged into:
d 2u
2
k12u ( r ) 0
dr
2m( E V0 )
With k1
2
51
and the solution is
u( r ) A sin k1r B cos k1r
To keep the wave function finite for r →0
u(r )
lim ( r ) lim 0
r0 r0 r
The coefficient B must be set to zero. Therefore the acceptable solution of physical
meaning is
u(r ) Asin k1r
II. When r > R
The Schrödinger’s equation is
2 d 2u
Eu ( r )
2m dr 2
the solution is
u( r ) Ce k2r De k2r
2mE
with k2
2
To keep the wave function finite for r →
lim u(r ) 0
r
The coefficient D must be set to zero. Therefore the acceptable solution of physical
meaning is
u(r ) Ce k2r
Applying the continuity conditions on u(r) and du/dr at r = R, we obtain
k1 cot k1 R k2
This transcendental equation gives a relationship between V0 and R.
From electron scattering experiments, the rms charge radius of the deuteron is
known to be about 2.0 fm. Taking R = 2.0 fm we may solve from above equation
the value of the potential depth V0. The result is V0 = 36 MeV. From the observed
binding energy, the size of the deuteron can be defined by 1 4.3 fm , which is
k2
52
about twice that of the range of the potential. This explains the fact that the
deuteron is a loosely bound state. (Its binding energy is 1.113 MeV per nucleon
compared with the average value of over 8 MeV per nucleon in nuclei.)
Since V0 E
cot k1 R k2 / k1 E / V0
Hence cot k1 R 0
3
k1 R , ,...
2 2
2 2 2 9 2
or V0 R 2 , ,...
4M 4M
u(r) cannot have a node inside the well, for this would indicate that u(r) and hence
wave function, is not the lowest (ground) energy level (Contradiction of our
hypothesis)
Hence only the first term retained, and
2 2 2
V0 R
4M
This relationship is known as Range depth relationship. The ground state wave
function together with the range and depth of the potential and the ground state
binding energy of the deuteron are shown in figure.
Figure 3
53
3.3
3.3Self
SelfLearning
LearningExercise-I
Exercise-I
Q.1 State clearly the definition of nuclear quadrupole moment.
Q.2 Draw three-dimensional square well nucleon-nucleon potential.
Q.3 Write down the basic properties of deuteron.
Q.4 Derive the range depth relationship of the Deuteron.
3.4
3.4Excited
ExcitedStates
StatesofofDeuteron
Deuteron
Extending the calculations of the bound state to cases where the orbital angular
quantum number l is greater than zero leads to a result that deuteron cannot exist in
these states. For the extreme case, binding energy EB~0, k1R is still only slightly
greater than /2, since the binding energy EB of the ground state has already been
found negligible compared to the potential well depth V0. For the first excited state
k1R would have to be greater than 3/2, since the wave function u(r) would have to
have a radial node inside the well. But from equation: k1R must certainly be less
than for all positive values of binding energy.
We shell here prove that for (l0) no bound state exists. It shall be assumed that
the potential is central and of square well type. The differential equation to be
used in this case (l0), is which through the substitution u ( r ) r ( r ) takes the
form
d 2u (r ) M l (l 1) h 2
E V ( r ) u ( r ) 0.
dr 2 h2 Mr 2
With r > R
Figure 4
54
On comparing these equations, we find that it is equivalent to an S-wave radial
equation with potential
l (l 1)h 2
Ve ff (r ) V (r )
Mr 2
The second term on R.H.S. is called the centrifugal potential as its space derivative
gives the classical centrifugal force. This potential is repulsive, there forces ‘l’
increases, the binding energy of the lowest bound state decreases.
Returning back to equation and setting l=1, the next acceptable value of l after 0,
we then get,
d 2u (r ) M 2h 2
2 2 u ( r ) 0.
dr 2 h Mr
Now E = -EB’ the binding energy of deuteron in the p state (l=1) and using a
square well potential V = V0’ for r < R, for the p- state, equation may be written as
d 2u ( r ) M ' 2h 2
for r < R 2 V0 EB ' u (r ) 0
dr 2 h Mr 2
d 2u ( r ) M 2h 2
and for r > R 2 EB u (r ) 0
dr 2 h Mr 2
Now letting
M
k1 ' 2 V0 '_ EB '
h
ME '
and k2 ' 2 B .
h
The above equation may be written as
d 2u(r ) 2 2
k1 ' 3 u ( r ) 0
dr 2 r
For r < R
d 2 u( r ) 2 2
and k2 ' 3 u(r ) 0
dr 2 r
for r>R
55
The least well depth, just repaired to produce this bound state, is the one for which
the binding energy EB’ is just equal to zero, i.e., when k2 ' 0 and
k1 ' MV '/ h k
0
2
0 (say).
If we put k0R= x, the wave equation reduces to
d 2u ( r ) 2u (r )
2
u (r ) 2 0
dx x
for x k0 R
d 2u (r ) 2u (r )
2 0
and dx 2 x
for x k0 R
The solution of equation with the correct boundary condition becomes
1
for x k0 R, u (r ) A2 x
To solve equation, we make the substitution v = xu(r), so that
dv du ( r )
x u
dx dx
d 2v d 2u(r ) du ( r )
and 2
x 2
2
dx dx dx
and it can then be re-written as follows
d 2 v 2 dv
for x k0 R. v 0
dx 3 x dx
Differentiating this equation with respect to x, we get
d 3v 2 d 2 v 2 dv dv
for x k0 R 0
dx 3 x dx 2 x 2 dx dx
Dividing this equation by x throughout , we get
1 d 3v 2 d 2 v 2 dv 1 dv
for x k0 R 0
x dx 3 x 2 dx 2 x 3 dx x dx
Now since
d 2 1 dv 1 d 3v 2 d 2 v 2 dv
dx 2 x dx x dx 3 x 2 dx 2 x 3 dx '
56
then the equation may be re-written as
d 2 1 dv 1 dv
for x k0 R 0
dx 2 x dx x dx
Now since u(r)=vx-1, must vanish for x = 0, the solution of above equation is found
to be
1 dv
for x < k0R. A1 sin x
x dx
Integrating it, we get
for x < k0R, v xu(r ) A1 (sin x x cos x)
To satisfy continuity condition at the boundary (r=R or x=k0R), these solutions
yields,
d
at x = k0R (sin x x cos x ) 0
dx
or x sin x = 0 at x = R
or k0R sin k0R = 0 at x = k0R
The smallest positive root of this equation is k0R = . Hence a bound state of the
deuteron for l 0 can exist only if k0R < and this contradicts the previous
statement that k0R ≃ . Therefore we conclude that no bound states exist for
deuteron when l 0, i.e., deuteron does not possess any excited state.
3.5
3.5Deuteron
DeuteronStructure
Structure
The deuteron is the only bound state of 2 nucleons, with isospin T = 0, spin-parity
= 1+, and binding energy EB=2.225 MeV. For two spin half nucleons, only total
spins S = 0, 1 are allowed. Then the orbital angular momentum is restricted to J − 1
< l < J + 1, i.e., l = 0, 1 or 2. Since the parity is π = (−) l = +, only l = 0 and l = 2
are allowed; this also implies that we have S = 1.
If the hamiltonian is
2 1 d 2 2 L2
H VC ( r ) VT ( r ) S12
M r dr 2 M r 2
using the following relation,
57
S12Y001 8Y211
S12Y211 8Y011 2Y211
L2Y011 0
L2Y211 6Y211
we find the radial equations
2 d 2
M dr 2 E Vc us 8VT uD
2 d2 6
dr 2 r 2 E 2VT Vc uD 8VT us
M
These equations can be solved numerically.
Other important information on the structure of the deuteron comes from the
values of the magnetic moment µ and quadrupole moment Q:
µ = 0.8574 µN
Q = 0.2857 e−fm2
Since Q0, the deuteron cannot be pure l = 0. But generally l = 0 is energetically
favored for a central potential. Therefore, we write the deuteron wave function as a
linear combination of S and D- waves
a 3S1 b 3 D1
T
[aR0Y011 bR2Y211 ] 00
where a and b are constants with a2+b2=1. R0 and R2 are the radial wave
functions, the isospin wave function is written as
1
T 00 [ p (1) n (2) n (1) p (2)]
2
3.6
3.6Magnetic
MagneticMoment
Moment
We first consider the implications of the magnetic moment. The magnetic moment
operator is
N ( g s szi g l l zi )
i
where gs = 4.7i + 0.88, where the first term is isovector, and the second term is
58
isoscalar. gl = (i + 1)/2. Since the deuteron is an iso-scalar particle, let us consider
only the iso-scalar magnetic moment. Then, the above equation becomes,
N (0.88szi 0.5l zi )
i
Note that since T = 0 only the isoscalar magnetic moment operator contributes to
µ:
2
N (0.88 S zi M 1
0.5 Lzi M 1
)
i 1
= N [0.88 S z 0.5 Lz ]
= N [0.88 S z 0.5M ]
= N [0.88 S z 0.5]
where we have used the fact that the sum of the two orbital angular momenta can
be decomposed into the sum of the center-of-mass angular momentum and relative
angular momentum. The center-of-mass angular momentum gives no contribution.
Let us now calculate the matrix element of Sz
Y `011 S z Y `011 1
Y `211 S z Y `011 1
2 1
Y `211 S z Y `211 | 2(1 M s )1M s |11 |
Ms 2
Thus, for pure l = 0 or l = 2 states we would have the values µ = 0.88µN, 0.31µN.
More generally we obtain the relation
[a 2 (0.88) b2 (0.31)] N (0.88 0.57b 2 ) N
Therefore, the experimental value µD = 0.857µN implies that b2 = 0.04. However, in
more sophisticated treatments one finds that it is quantitatively important to
explicitly include the effects of meson exchanges on the magnetic moment.
3.7Quadrupole
3.7 QuadrupoleMoment
Moment
Now we consider the quadrupole moment of the deuteron. Using the definition of
16 * 2 3i 1 2
Qe ri Y20 J M 1d 3r
5 J M 1
i 1 2
16 * ri 2
Y20 J M 1d 3r
5 J M 1 4
=e
59
Here we have used the fact that for each nucleon the distance from the center of
mass is only half the distance between them, ri= r/2. Now using the expressions for
the wave function introduced above
2 2
| a2 | r R02 r 2 dr Y00* Y20Y00d 2 Re(ab* ) r R0 R2 r 2 dr
4
4
16
Qe S 1, M s 1 S 1, M s 1 M Y00* Y20Y2 M d 1(1 M 2M ) 11
5 M
r 2
+|b2 | R22 r 2 dr 1(1 M )2M 11 Y2*M Y20Y2 M d
4 M
After evaluating the angular integrals and putting in the CG coefficients, one finds
16 2 4 | b2 | 4 2
Qe Re(ab*) r R0 R2 dr
20
r R2 dr
5 10
To proceed further we need to evaluate the radial integrals, so we would need to
solve the radial Schrodinger equation and obtain the radial wave functions. Clearly,
for a given potential model this is (in principle) possible. For our purposes, we will
use our knowledge that b = 0.2 ≪ 1 from the magnetic moment analysis and keep
only the first term. This will give us an approximate expression that we can set
equal to the experimental value Qexp = 0.286 e fm2 to obtain the result
0.2 2 4
Qe r R0 R2 dr 0.286efm 2
10
Solving for the unknown radial integral yields
4 2
r R R dr 10.1 fm
0 2
for the radial integral. This value seems quite reasonable given that the mean
squared charge radius of the deuteron is 4.0 fm2.
To elucidate the effect of the tensor (non central) force on the structure of the
deuteron let’s consider the quadrupole moment, for which we need to use the M =
60
1 state. The dominant S-D interference term in the quadrupole moment has MS = 1.
So the spins of both the two nucleons are predominantly aligned parallel to z. Let’s
simply take σ1 = σ2 = +z, and then σ1·σ2 = +1. Then we need to consider the
relative orientation of r, and we will focus (see Fig. on two extreme cases: (a) r||z
and (b) r ⊥ z).
In case
(a) σ1·r = σ2·r = 1, so we have S12 = +2 for this geometrical arrangement. This is
a prolate configuration so we expect Q > 0 for case (a).
(b) In case (b) we have σ1 · r =σ2 · r = 0 so S12 = −1 and the oblate shape relative
to the z axis would imply Q < 0.
Since experimentally Q > 0, case (a) must be energetically favored which
corresponds to VT(r)<0. This then gives an attractive force when the configuration
is such that S12 > 0 (case (a)) and a repulsive force when S12 < 0 (case (b)).
Given VC(r) and VT(r), this is an eigenvalue problem for k2 with a free parameter to
be determined: the ratio b/a. It was shown by Rarita and Schwinger that large class
of potentials can solve these equations with the constraints EB = 2.225 MeV and
Q = 0.286e-fm2.
3.8
3.8Self
SelfLearning
LearningExercise-II
Exercise-II
Q.1 Define magnetic moment.
Q.2 Explain that “no bound states exist for deuteron”.
Q.3 Calculate the magnetic and Quadrupole moment of Deuteron.
3.9
3.9Answer
AnswertotoSelf
SelfLearning
LearningExercise
Exercise
Answer to Self Learning Exercise-I
Ans.1: See Glossary
Answer to Self Learning Exercise-II
Ans.2: See Glossary
3.10
3.10Exercise
Exercise
Q.1 Solve the Schrodinger equation for the deuteron in a S-state under the
61
assumption of square well potential.
Q.2 Show that deuteron has the D-state admixture
3.11
3.11Summary
Summary
After going through this chapter, you would be able to achieve the aforesaid
objectives. Now we recall what we have discussed so far.
We have learnt the basic properties of deutron, its charge (+e), mass (~2.014
amu), its radius (2.1 fermi), its binding energy (=2.225 .003 Mev), Spin and
statistics (Bose-Einstein) and the electric quadrupole moment Qd =0.00282
barn.
The study of deuteron problem, although hopelessly limited in as much as
deutron possesses only the ground state and no-excited states exist for the
bound neutron-proton system, gives invaluable clues about the nature of the
nuclear force.
We learnt that neutron and proton can form stable combination (deuteron) only
in the triplet state means when the n & p spins are parallel. The singlet state,
i.e. a state of antiparallel n-p spins being unbound.
The existence of non-zero magnetic moment and electric quadrupole moment
for deutron suggests that at least a part of the neutron proton force acting in
deutron is non-central.
3.12
3.12Glossary
Glossary
Barn: A unit of cross-section, a barn is equal to 10-28 m2.
Cross-section: a measure of the likelihood of a given process occurring at an
accelerator. The idea is that two objects with a larger cross-sectional area are more
likely to hit one another. So, larger cross-sections mean that a process is more
likely to occur. Cross-sections are measured in barns, 10-28 m2. A barn is an
extremely large cross-section in particle physics. Many interesting cross-sections
are measured in pb (picobarns), which are equal to 10-12 barns.
The magnetic moment: (or magnetic dipole moment) of an object is a measure of
the object's tendency to align with a magnetic field. It is a vector quantity, with the
62
positive direction defined by the way the object responds to a magnetic field: The
object will tend to align itself so that its magnetic moment vector is parallel to the
magnetic field lines. There are two sources for a magnetic moment: the motion of
electric charge and spin angular momentum. For example, a loop of wire with a
current running through it will have a magnetic moment proportional to the current
and area of the loop, pointing in the direction of your right thumb if your fingers
are curling in the direction of the current. Alternatively, an electron, which is a
spin-1/2 fermion, has an intrinsic magnetic moment proportional to its spin.
Quadrupole Moment: the quantity that characterizes the deviation from spherical
symmetry of the electrical charge distribution in an atomic nucleus. It has the
dimension of area and is usually expressed in sq cm. For spherical symmetry the
nuclear quadrupole moment Q = 0. If a nucleus is extended along the axis of
symmetry, then Q is a positive quantity, but if the nucleus is flattened along the
axis, it is negative. The value of the nuclear quadrupole moment varies over a wide
range.
References
Referencesand
andSuggested
SuggestedReadings
Readings
1. “The Two Nucleon Problem” by M. Sugrwara and Hulthen.
2. “Nuclear Two Body Problems and Elements of Nuclear Forces” Experimental
Nuclear Physics by N. F. Ramsey.
3. Lectures on Nuclear Theory by Landau, Plenum.
4. Elementary Nuclear Theory, 2nd ed. by Bethe and Morrison.
5. The Atomic Nucleus by R D. Evans.
6. Atomic and Nuclear Physics by Brijlal and Subhraininyan.
7. Nuclear Physics by D. C Tayal.
8. Nuclear Physics by Irving Kaplan
63
UNIT-4
Nucleon-Nucleon Scattering
and Potentials: Part-I
Structure of the Unit
4.0 Objectives
4.1 Introduction
4.2 Neutron-proton scattering at low energy assuming central potential with
square well shape
4.3 Results of low energy n- p scattering
4.4 Self learning exercise-I
4.5 Spin dependence and scattering length
4.6 Coherent scattering of neutrons by protons in ortho and Para hydrogen
molecules
4.7 Conclusions of these analysis regarding scattering lengths
4.8 Self learning exercise II
4.9 Summary
4.10 Glossary
4.11 Answers to self learning exercises
4.12 Exercise
References and Suggested Readings
4.0
4.0Objectives
Objectives
After interacting with the material presented here students will be able to
Learn n-p scattering at low energies with specific square well potential.
Comparatively study the results of low energy n-p scattering.
Know the spin dependence and scattering length.
64
4.1
4.1Introduction
Introduction
Having ascertained that nuclei are quantum mechanical systems composed of
nucleons, it is quite plausible to study the nuclear forces under the simplest
possible conditions. The simplest case in which the nuclear force is effective is
when:
1. When the two nucleons are bound together.The three possible bound states of
a two nucleon system, di-neutron (nn), di-proton (pp) and deuteron (np),
nature has provided us with only the deuteron and the other two are unstable.
2. When the two nucleons are in free state and one is made to impinge on the
other, i.e. The scattering processes.
In practice, it is not possible to make a neutron target and therefore scattering
experiments are limited only to neutron proton (np) scattering and proton-
proton (pp) scattering.
The first case we discussed in previous chapter and second case we will discuss in
our upcoming two chapters. In this chapter we will focus only on np scattering.
The first question arises in our mind is that, What is Scattering? The answer is,
when an intense and collimated beam of nucleons is born barded on target nuclei
the interactions between incident nucleus and target nuclei takes place. As a result
we may observe the following two possibilities:
1. The interaction does not change the incident particles, i.e., incoming and
outgoing particles are the same. The change is in the path of incoming
nucleons, i.e., they are deviated from their original path. This process is known
as scattering, In scattering processes the outgoing particles may have same
energy as that of incident particles or may have the changed energy value. The
former is known as elastic scattering and latter is known as inelastic scattering.
2. The second possibility is that the outgoing particles are different from the
incident particles. Then the interaction process is known as nuclear reaction. In
nuclear reaction we have two alternatives:
It should be remembered that any of the above alternative may occur, either
alone or with other competing processes.
Among the nucleon-nucleon scattering, neutron proton (n-p) scattering is the
65
simplest one, because here the complications due to coulomb forces are not
present. The neutron neutron (n-n) scattering is not practically possible because of
the non availability of neutron target (because neutron decays into proton in a few
minutes). However, their are evidences to support if n-n forces are similar to p-p
forces, a bound state for two neutrons cannot exist.
4.2
4.2 Neutron-Proton
Neutron-Proton Scattering
Scattering at Low Energy
Energy assuming
assuming
Central
CentralPotential
Potentialwith
withSquare
SquareWell
WellShape
Shape
In np scattering neutron proton system is analyzed in the state of positive energy,
i.e., in a situation when they are free. In the experiment, a beam of neutrons from
an accelerator is allowed to impinge on a target containing many essentially free
protons. The simplest substance is hydrogen gas but in some cases other substances
like thin nylon sheet and paraffin are used. Hence, it is natural to think that in
target protons are not free but are bound in molecules. The molecular binding
energy is so small about 1eV, therefore, for the impinging neutrons of energy
greater than 1eV, protons are treated as free. The presence of electrons also do not
affect the process because they are too light to cause any appreciable trouble to
incoming neutrons. When neutrons impinge on protons, some of them are captured
to form deuteron and balance of energy is radiated in the form of rays; but the
great majority of neutrons undergo elastic scattering. In the process, the interaction
between two nucleons is of such an order that the neutrons changed their velocities
in magnitude as well as in direction.
Neutron – Proton Scattering at Low Energies
In the low energy range most of the measurements of scattering cross
section are due to Melkonian and Rainwater et.al. A beryllium target bombarded at
by deuterons accelerated in a cyclotron, provided the neutron beam which was shot
at a target containing free protons.
Results from figure 1 show that the scattering cross section depends very much on
the energy of the incident neutrons. At low energies below 10 Mev, the scattering
is essentially due to neutrons having zero angular momentum (l=0) and hence in
the centre of mass system, the angular distribution of scattered neutrons is
isotropic. In order to avoid complications due to Coulomb forces we shall consider
66
the scattering of neutrons by free protons viz. those not bound to molecules.
However in practice the protons are of course bound to molecules but the
molecular binding energy is only about 0.1 ev. Therefore if the incident neutrons
have an energy greater than about 1ev. The protons can be regarded as free.
Figure 1: np scattering cross section
In describing elastic scattering events like the scattering of neutrons by free
protons it is more convenient to use the center of mass system. The quantum
mechanical problem describing the interaction between two particles, in the center
of mass system, is equivalent to the problem of interaction between a reduced mass
such as the system. Although while wording out the following theory we shall
think in terms of a neutron being scattered by a proton but it applies equally well to
spin less, reduced mass particle which is being scattered by a fixed force center.
Let us suppose that the neutron and the proton interact via a spherically symmetric
force field whose potential function is V (r), where r is the distance between the
particles.
The Schrodinger equation for a central potential V (r) in the center of mass system,
for the n-p system is
2 M
h 2 E V (r ) 0
Where M is the reduce mass of the n-p system.
To analyze the scattering event, we have to solve this equation under proper
boundary conditions. In the immediate vicinity of the scattering center, the action
67
will be violent and its description is difficult. At a considerable distance from the
scattering center where the experimentalist lies in wait for the scattered particles,
things will however be simpler. For scattering the boundary condition is that at
large distances from the scattering center the wave should be made up of two parts:
1. an incident plane wave that describes the unscattered particles and super-
imposed upon it,
2. an outgoing scattered spherical wave which emanates from the scattering
center. To solve in asymptotic form,
inc sc
The wave function that describes an incident plane wave (a beam of particles)
moving in the positive z-direction is
inc eikz eikz cos ,
ME
Where k 2
h
which is a solution of the wave equation with V(r) set equation zero,
2 ME
h 2 inc 0,
Setting V(r) equal to zero in this manner actually amounts to switching off the
scattering potential and there by eliminate scattering so that the total wave function
becomes identical with the incident wave function. The wave function represents
one particle per unit volume since the square of the wave function is equal to unity.
Having known the form of the incident wave function, the next problem is to
devise a suitable form for the scattered wave function. This obviously is
e ikr
sc f ,
r
For large r f( ) in this expression indicate amplitude of the scattered wave in the
direction . This wave function is a necessary consequence of the assumption that
the scatterer simply scatters the particles and does not absorb them at all.
The probability density and hence the number of scattered particles per unit
volume shall be proportional to sc 2 . If scattering is considered to be isotropic,
the density (number per unit volume) of scattered particles through a large
spherical shell of radius r is inversely proportional to r2 since the volume of the
68
spherical shell, being given by 4r 2 dr, is proportional to r2 and density therefore is
2
proportional to 1/r2 which is also proportional to sc . Hence 1/r2 dependence of
sc .
Therefore the wave function, in a form we are actually interested viz. asymptotic,
ikz eikr
may be written as. inc sc e f .
r
Now, in Fourier analysis we often expand as arbitrary function into a sense of
harmonic functions of various frequencies. So we expand the incident plane wave
function eikz in terms of Legendre Polynomials Pl (cos) and write.
ikrcos
inc e Bl (r ) Pl cos
l 0
where l is an integer representing the various partial waves. This particular way of
writing the wave function is termed as the partial wave expansion.
The radial functions B1(r) in this equation are given by
Bl (r ) i l (2l 1) jl (kr ),
Where Jl(kr) is the Spherical Bassel function which is related to the ordinary
Bessel function through the formula
1/ 2
jl (kr ) J l 1/ 2 (kr )
2kr
l
1 d sin kr
and can be represented as jl ( kr ) ( kr ) l
kr d ( kr ) kr
Whence asymptotically
l
sin kr
2
jl (kr ) r
kr
Asymptotically, Bl(r) from is given by
l
sin kr
2
Bl (r ) r i l (2l 1)
kr
69
1 l
2ikr
i (2l 1). ei ( kr l / 2) e
i ( krl / 2 )
.
The Spherical Bessel function Jl(kr) for various values of l are given below
3 1 3 cos(kr )
j2 (kr) sin(kr ) .
3
(kr ) kr kr 2
These functions are plotted in the Fig.
Similarly f() may also be expanded in terms of the Legendre Polynomials as
follows
i
f ( ) f1 (2l 1) P1 (cos ).
2k l o
Substituting from equation in equation we obtain
e ikr
inc sc i l ( 2l 1) jl ( kr ) f l P1 (cos ).
l 0 r
Since each term in the equation with a specific value of the orbital angular
momentum quantum number l, represents a solution of the wave equation in
spherical polar co-ordinates for constant potential energy. Therefore the expansion
70
classifies the particles in the beam according to their angular momenta which is of
great practical importance since at lower energies below 10 Mev, most of the
scattering is due to l=0 particles, i.e. the number of partial waves is severely
limited in this case and it suffices to study the scattering only for l=0, i.e. S-wave.
For l=0
B (r )
sin(kr )
1
kr 2 .......
0
kr 6
and for l=1
sin(kr ) cos(kr )
B1 (r ) 3i
kr kr
kr kr 3
3i .......
3 30
B1 ( r )
( kr ) 2 .
B0 ( r )
We have found out the ratio of the square, since the probability density is
determined by Bl2(r). To have an idea of the magnitude of this ratio, let us consider
a neutron of energy 1 Mev in the L-system, it will be 0.5 Mev in the C-M system.
Neutron momentum then is
1
2 1.67 10 24 1.6 10 6
p ( 2ME ) 2
2
1.63 10 15 gm.cm. / sec .
p 1.631015 12 1
and its wave number k 1.55 10 cm.
h 1.05451027
If we assume the nuclear forces to have a range r = 2 Fermi, then
2
B1 (r ) 2
(kr ) 2 1.551012 2 1013 0.31 = 0.0961,
B0 (r )
i.e. at an energy of 1 Mev only about 9% of the scattering is due to neutrons with
l=1. Similar calculation for a neutron of energy 10 Mev raises this percentage to
about 49%. Therefore in the energy range below 10 Mev. S-wave scattering (l=0)
is predominant.
71
4.3
4.3Results
ResultsofofLow
LowEnergy
Energyn-p
n-pScattering
Scattering
The theory for the scattering cross-section developed in the previous section is in
fact a theory for the phase shift l which in turn depends up on the assumptions
regarding the nature of the scattering potential V(r). We now proceed to carry out
the calculations for the same rectangular potential well as was assumed in sections
for the deuteron ground state.
The radial Schrodinger equation for l=0, viz. equation inside and outside the
nuclear square potential well may be written as
d 2u (r ) M
2 E V0 u (r ) for r < r0,
dr 2 h
d 2 u (r ) M
2 Eu(r ) 0 for r > r0,
dr 2 h
Since in the present case of n-p scattering, the negative binding energy is replaced
by a small positive energy E which is much smaller than the well-depth V0. These
equation may be written as
d 2 ui
2
K 2 ui 0 for r < r0,
dr
d 2 u0
2
k 2 u0 0 for r > r0,
dr
Where ui is the wave function inside the well and u0 that outside the well and
M ( E V0) ME
K2 ,k2 .
h h2
Equation has the solution ui A sin Kr
And equation has the solution u0 C sin kr D cos kr ,
Which may be written as u0 B sin( kr 0 ).
In order to understand the significance of the phase shift 0 , the Schrodinger
equation would be equation V(r) set equal to zero, the solution of which would
have to be of the form
u (r ) sin kr.
Since it must vanish at r= o. The solution which holds good only outside the well.
Thus 0 is the phase shift at large distances introduced by switching on the
72
scattering potential.
We now require that the solution and join smoothly at r = r0 i.e. the logarithmic
derivative must be continuous at r=r0 viz,
1 dui 1 du0
r r0
ui dr u0 dr r r0
This condition, with the aid of equation gives
K cot Kro k cot( kr0 0 )
This result may be compared with the continuity condition equation for the ground
state of the deuteron viz.
M (V0 EB ) M (V EB )
cot
0
r0
h h
MEB
where
2
To simplify the matching condition in case of n-p scattering, we assume that inside
the well, the scattering wave function is not much different from the deuteron wave
function. This appears quite reasonable since the two situations differ only in that
the total energy E in this case although small, is positive whereas the deuteron
binding energy EB is small, but negative. We therefore assume that the logarithmic
derivative KcotKr0 of the inside wave function for scattering could be
approximated by the value of the logarithmic derivative of the ground state wave
function of deuteron viz. . Hence from
k cot kr0 0
At this point we introduce another approximation that r0 is very small (possibly
zero) compared to k ( MF / h) so that kr0 may be neglected in the above
equation and then
k cot 0 or cot 0 / k
Now the total scattering cross-section for l=0 from equation is given by
4 4 1 4 1
sc ,0 2
sin 2 0 2 . 2.
k k (1 cot 0 ) k (1 γ 2 / k 2 )
2
73
4 4h 2
2 2
.
k M ( E EB )
where we have substituted the values of k2 and 2 from equations and respectively.
4.4Self
4.4 SelfLearning
LearningExercise-I
Exercise-I
Q.1 What is Scattering?
Q.2 Draw a neutron proton scattering cross section graph.
Q.3 Write down the Schrodinger equation, for the n-p system, for a central
potential V (r) in the center of mass system.
Q.4 Discuss in detail the results of low energy np scattering.
4.5
4.5Spin
SpinDependence
Dependenceand
andScattering
ScatteringLength
Length
Spin dependence:
E. P. Wigner suggested that the inter-nucleon forces are spin-dependent. Since
neutron and proton are 1 spin particles, therefore in n-p scattering the neutron and
2
proton spins may either be parallel or anti parallel. In deuteron the bound state of
the n-p system, whose binding energy EB, the neutron and proton spins are parallel
and therefore this equation possibly holds good for parallel spin case.
The state of parallel spins, is a triple state and has a statistical weight 3
corresponding to the three allowed orientations of the angular momentum vector
under an external magnetic field. The state of anti parallel spins is a singlet state on
account of the non orientability of a vector of zero length and has a statistical
weight.
In a scattering experiment in general neutron and proton spins are randomly
oriented and so are the spins of neutrons in the incident beam and therefore singlet
and triplet state of the n-p system will occur in proportion to the statistical weight
factors for these states which are 1 and 3
respectively. The total scattering cross-
2 4
section therefore shall be made up of two parts, t ,0 - the cross-section for
scattering in the triplet state and s ,0 the scattering cross-section in the singlet
state, as follows
74
3 1
0 t ,0 s ,0
4 4
We therefore take t= 4.6 b and using the measured value of = 20.4 b for the
low-energy cross section, we deduce
s = 67.8 b
This calculation indicates that there is an enormous difference between the cross
sections in the singlet and triplet states that is, the nuclear force must be spin
dependent.
From a naïve point of view, in a random distribution of spins as in n-p scattering,
the two spins are as often parallel as antiparallel giving equal statistical weights to
the two states. However quantum mechanically, the spin direction cannot be
defined as uniquely as a vector in space and hence the statement ‘spin pointing up’
simply tells that the spin vector points somewhere along a cone around the vertical
direction. The following figure depicts schematically the four equally likely
situations for the relative spins of the two particles.
(1)
(2)
(3)
(4)
75
Figures (1) and (4) correspond to a total spin unity corresponding to the magnetic
quantum number values +1 and -1 respectively. In cases (2) and (3) the z-
components add up to zero but since the spins are not aligned along the z-direction,
they may add up to zero as in case (2) resulting in a singlet state or may add up to a
total spin perpendicular to the z-axis as in case (3) giving rise to a triplet state.
Scattering Length:
Fermi and Marshall introduced a very useful concept the ‘scattering length a’ for
the discussion of nuclear scattering at very low incident neutron energy.
ME
[i.e.E 0 and hence k 2 0
h
which is defined as follows:
sin 0
a Lim ;
k 0
k
With this definition, equation giving the total scattering cross section form S-wave
(l=0) may be written for very low incident neutron energy as
4 sin 2 0 2
Lim sc Lim 2 4 a
k 0 k 0
k
Equation then indicates that ‘a’ has the geometrical significance of being the radius
of a hard sphere surrounding the scattering center from which neutrons are
scattered and so has the dimensions of length, hence the name scattering length.
Now it is to be noted from equation that as k 0 (i.e.,) as the energy E of the
incident neutron approaches 0, must approach either 0 or otherwise the cross-
section at zero neutron energy would become infinite which is physically absurd.
Therefore at very low incident neutron energies ( E 0 ), equation reduces to
0
a
k
Then at very low incident neutron energies, the wave function outside the range of
nuclear force as expressed by equation may be written as
sin( kr 0
Lim u (r ) Lim(r 0 ) Lim e i 0
k 0 k 0 k 0
k
76
The equation then gives a simple graphical interpretation of the scattering length.
This equation represents a straight line for U(r) and the scattering length ‘a’ is the
intercept on the r-axis. This is indicated in Figure.
Having defined the scattering length by means of equations an inquisitive reader
may ask quite naturally what is the significance of positive or negative scattering
length ? or what is the significance of attaching a positive or a negative sign with
at the scattering length? It tells us whether the system has a bound or an unbound
state.
From figure it is clear that positive scattering length indicates a bound state and
negative scattering length indicates a virtual or unbound state. Since the deuteron
wave unction, i.e., the wave function for the bound state of n-p system, must curve
towards the r-axis in order to match the exponentially decaying solution (c.f.
equation i.e. r >r0 will give rise to a positive intercept on the r-axis indicating
thereby a positive scattering length. For unbound state the wave function has to
match with an increasing solution outside the range r0 and then extrapolation of
U(r) shall produce a negative intercept on the r-axis implying thereby a negative
scattering length.
4.6 of Neutrons
4.6 Coherent Scattering of Neutrons by
by Protons
Protons inin Ortho
Ortho
and Para
ParaHydrogen
HydrogenMolecules
Molecules
We can verify our conclusions about the singlet and triplet cross sections in a
variety of ways. One method is to scatter very low energy neutrons from hydrogen
77
molecules. Molecular hydrogen has two forms, known as orthohydrogen and
parahydrogen. In orthohydrogen the two proton spins are parallel, while in
parahydrogen they are antiparallel. The difference between the neutron scattering
cross sections of ortho- and parahydrogen is evidence of the spin-dependent part of
the nucleon-nucleon force. Our discussion of the cross section for neutron-proton
scattenng is inadequate for analysis of scattering of neutrons from H2 molecules.
Very low energy neutrons (E < 0.01 eV) have a de Broglie wavelength larger than
0.05 nm, thus greater than the separation of the two protons in H2. The uncertainty
principle requires that the size of the wave packet that describes a particle be no
smaller than its de Broglie wavelength. Thus the wave packet of the incident
neutron overlaps simultaneously with both protons in H2, even though the range of
the nuclear force of the individual neutron-proton interactions remains of the order
of 1 fm. The scattered neutron waves 1 and 2 from the two protons will
therefore combine coherently; that is, they will interfere, and the cross section
depends on |1 + 2|2, not |1|2 + |2|2. We cannot therefore simply add the
cross sections from the two individual scatterings. (At higher energy, where the de
Broglie wavelength would be small compared with the separation of the protons,
the scattered waves would not interfere and we could indeed add the cross sections
directly. The reason for choosing to work at very low energy is partly to observe
the interference effect and partly to prevent the neutron from transferring enough
energy to the H2 molecule to start it rotating, which would complicate the analysis.
The minimum rotational energy is about 0.015 eV, and so neutrons with energies
in the range of 0.01 eV do not excite rotational states of the molecule.)
4.7 Conclusions
4.7 Conclusions ofof these Analysis
Analysis regarding
regarding Scattering
Scattering
Lengths
Lengths
To analyze the interference effect in problems of this sort, we introduce the
scattering length a, defined such that the low-energy cross section is equal to 4a2
lim k 0 4 a 2
sin 0
a limk 0
k
The choice of sign is arbitrary, but it is conventional to choose the minus sign.
78
Even though the scattering length has the dimension of length, It is a parameter
that represents the strength of the scattering, not its range. To see this, we note
from above equation that 0 must approach 0 at low energy in order that a remain
finite. The scattered wave function can be written for small 0 as
0 eikr eikr
scattered A Aa
k r r
Thus a gives in effect the amplitude of the scattered wave.
The sign of the scattering length also carries physical information. Figure shows
representations of the triplet and singlet scattered wave functions u(r). The triplet
wave function for r < R looks just like the bound state wave function for the
deuteron: u(r) "turns over" for r < R to form the bound state. The value of at is
therefore positive. Because there is no singlet bound state, u(r) does not turn over
for r < R, so It reaches the boundary at r = R with positive slope When we make
the smooth connection at r = R to the wave function beyond the potential and
extrapolate to u(r) = 0, we find that as, the singlet scattering length, is negative.
Our estimate t = 4.6 b from the properties of the deuteron leads to at = + 6.1m,
and the estimate of s = 67.8b needed to reproduce the observed total cross section
gives as = -23.2 fm.
The theory of neutron scattering from ortho and parahydrogen gives
para =5.7(3at + as )2
ortho = para + 12.9(at - as )2
where the numerical coefficients depend on the speed of the incident neutron.
79
The measured cross sections corrected for absorption, for neutrons of this speed are
para = 3.2 ± 0.2 b and ortho = 108 ±1 b. If the nuclear force were independent of
spin, we would have t = s and thus at = as; thus para and ortho would be the
same. The great difference between the measured values shows that at as, and it
also suggests that at and as must have different signs, so that - 3at = as in order to
make para small. Solving equations for as and at gives
as = -23.55 ± 0.12 fm
at = +5.35 ± 0.06 fm
consistent with the values deduced previously from t and s. There are several
other experiments that are sensitive to the singlet and triplet scattering lengths;
these include neutron diffraction by crystals that contain hydrogen (such as
hydrides) as well as the total reflection of neutron beams at small angles from
hydrogen-rich materials (such as hydrocarbons). These techniques give results in
good agreement with the above values for as and at".
The theory we have outlined is valid only for l = 0 scattering of low-energy
incident particles. The l = 0 restriction required particles of incident energies below
20 MeV, while our other low energy approximations required eV or keV energies.
As we increase the energy of the incident particle, we will violate long before
we reach energies of 20 MeV. We therefore still have l= 0 scattering, but at these
0 eikr eikr
energies (of order 1 MeV) equations scattered A Aa are not valid.
k r r
This case is generally treated in the effective range approximation, in which we
take
k cot 0 = 1/a + 1/2 r0k2 + ...
and where terms in higher powers of k are neglected. The quantity a is the zero-
energy scattering length we already defined (and, in fact, this reduces to
sin 0
a limk 0 in the k ~ 0 limit), and the quantity r0 is a new parameter, the
k
effective range. One of the advantages of this representation is that a and r0
characterize the nuclear potential independent of its shape; that is; we could repeat
all of the calculations done in this section with a potential other than the square
80
well, and we would deduce identical values of a and r0 from analyzing the
experimental cross sections. Of course there is an accompanying disadvantage in
that we can learn little about the shape of the nuclear potential from an analysis in
which calculations with different potentials give identical results!
Like the scattering lengths, the effective range is different for singlet and triplet
states. From a variety of scattering experiments we can deduce the best set of l= 0
parameters for the neutron-proton interaction:
as = -23.715 ± 0.015 fm
r0s = 2.73 ± 0.03 fm
at = 5.423 ± 0.005 fm
r0t = 1.748 ± 0.006 fm
As a final comment regarding the singlet and triplet neutron-proton interactions,
we can try to estimate the energy of the singlet n-p state relative to the bound
triplet state at - 2.22 MeV. Using Equations we would deduce that the energy of the
singlet state is about + 77 keV. Thus the singlet state is only slightly unbound.
4.8
4.8Self
SelfLearning
LearningExercise
ExerciseIIII
Q.1 Which state is known as triplet state.
Q.2 Define scattering length and its physical significance.
Q.3 Explain that the nuclear force must be spin dependent.
Q.4 Discuss Coherent scattering of neutrons by protons in ortho and Para
hydrogen molecules.
4.9
4.9Summary
Summary
In this chapter we have discussed n-p scattering at low energies with square well
potential. We also discussed that the nuclear forces are spin dependent i.e., nuclear
forces not only depend upon the separation distance but also upon the spin
orientations of two nucleons. They are independent of the shape of nuclear
potential.
4.10Glossary
4.10 Glossary
Angular Momentum : A measure of the momentum of a body in rotational
81
motion about its centre of mass. Technically, the angular momentum of a body is
equal to the mass of the body multiplied by the cross product of the position vector
of the particle with its velocity vector. The angular momentum of a system is the
sum of the angular momenta of its constituent particles, and this total is conserved
unless acted on by an outside force.
Neutron : One of the two main building blocks (along with the proton) of the
nucleus at the centre of an atom. Neutrons have essentially the same mass as a
proton (very slightly larger) but no electric charge, and are made up of one “up”
quark and two “down”quarks. The number of neutrons in an atom determines
theisotope of an element. Outside of a nucleus, they are unstable and disintegrate
within about ten minutes.
Nucleus: The tight cluster of nucleons (positively-charged protons and zero-
charged neutrons, or just a singleproton in the case of hydrogen) at the centre of an
atom, containing more than 99.9% of the atom’smass. The nucleus of a typical
atom is about 100,000 smaller than the total size of the atom(depending on the
individual atom).
Proton : One of the two main building blocks (along with the neutron) of the
nucleus at the centre of an atom. Protons carry a positive electrical charge, equal
and opposite to that of electrons, and are made up of two “up” quarks and one
“down” quark. The number of protons in an atom’s nucleus determines its atomic
number and thus which chemical element it represents.
Spin: Spin is a characteristic property of elementary particles
4.11
4.11Answers
AnswerstotoSelf
SelfLearning
LearningExercise
Exercise
Answers to Self Learning Exercise-I
Ans.1: When an intense and collimated beam of nucleons is born barded on target
nuclei the interactions between incident nucleus and target nuclei takes
place. The interaction does not change the incident particles, i.e., incoming
and outgoing particles are the same. The change is in the path of incoming
nucleons, i.e., they are deviated from their original path. This process is
known as scattering
Ans.2: section 4.2
82
M
Ans.3: 2 2
E V (r ) 0
h
Answers to Self Learning Exercise-II
Ans.1: The state of parallel spins is called triplet state.
Ans.2: ‘a’ has the geometrical significance of being the radius of a hard sphere
surrounding the scattering center from which neutrons are scattered and so
has the dimensions of length, hence the name scattering length.
sin 0
a Lim ;
k 0
k
3 1
Ans.3: 0 t ,0 s ,0
4 4
where t= 4.6 b and = 20.4 b (for the low-energy cross section), we
deduce s = 67.8 b
This calculation indicates that there is an enormous difference between the
cross sections in the singlet and triplet states that is, the nuclear force must
be spin dependent.
4.12
4.12Exercise
Exercise
Q.1 Write short note on scattering length.
Q.2 Discuss Neutron-proton scattering at low energy.
References
Referencesand
andSuggested
SuggestedReadings
Readings
1. Elementary Nuclear Theory by Bethe and Morrison.
2. The Atomic Nucleus by R D. Evans.
3. Atomic and Nuclear Physics by Brijlal and Subhraininyan.
4. Nuclear Physics by D. C Tayal.
5. Nuclear Physics by Irving Kaplan.
6. Introductory Nuclear Physics by Kenneth S. Krane
83
UNIT-5
Nucleon-Nucleon Scattering
and Potentials
Potentials:: Part-II
Part-II
Structure of the Unit
5.0 Objectives
5.1 Introduction
5.2 Boson Exchange Potentials
5.3 Basic Potentials
5.4 Hamada-Johnston Potential
5.5 Yale-Group Potential
5.6 Reid68 and Reid-Day Potentials
5.7 Self learning exercise I
5.8 One Boson Exchange Potential
5.9 Self learning exercise II
5.10 Summary
5.11 Glossary
5.12 Answers to self learning exercises
5.13 Exercise
References and Suggested Readings
5.0
5.0Objectives
Objectives
After interacting with the material presented here students will be able to
understand
Hamada- Johnston hard core potential
Reid hard core and soft core potentials and
One boson Exchange Potentials
84
5.1
5.1Introduction
Introduction
The interaction between two nucleons is basic for all of Nuclear Physics. The
traditional goal of Nuclear Physics is to understand properties of atomic nuclei in
terms of the "bare" interaction between pairs of nucleons. With starting of
Quantum Chromo Dynamics (QCD), it became clear that the NN interaction is not
fundamental. Nevertheless, even today, in any approach towards a nuclear
structure problem, one assumes the nucleons to be elementary particles. The failure
or success of this approach may then teach us something about the relevance of sub
nuclear degrees of freedom. A large number of physicists, all over the world, have
investigated the NN interaction for the past 70 years. This interaction is the
empirically best known piece of strong interactions; in fact, for no other sample of
strong force a comparable amount of experimental data has been accumulated. The
oldest attempt to explain the nature of the nuclear force is due to Yukawa.
According to this theory massive bosons (mesons), mediate the interaction between
two nucleons. Although, in the light of QCD, meson theory is not perceived as
fundamental anymore, the meson exchange concept continues to represent the best
working model for a quantitative Nucleon-Nucleon potential. Most basic questions
were settled in the 1960's and 70's such that in recent years we could concentrate
on the subtleties of this peculiar force.
5.2
5.2Boson
BosonExchange
ExchangePotentials
Potentials
The potential acting between a pair of particles due to the exchange of a meson has
a range of the order of the meson Compton wavelength that is inversely
proportional to the meson mass. Since the π meson is the lightest boson that can
be exchanged between a pair of nucleons, the OPEP determines the long-range part
(beyond the pion Compton wavelength) of the two-nucleon potential. If one wants
information on the two-nucleon potential at intermediate- and short-ranges, one is
then faced with the computation of the potential arising from the exchange of the
heavier bosons and two, three,… pions. Since this computation is comparatively
more difficult, thus at the potentials constructed based on symmetries (e.g., Breit
and coworkers potential), it is determined phenomenologically; while at the meson
theory of the two-nucleon potential, these exchanges are considered explicitly. It is
understood that multi-meson systems most often have strongly correlated
85
resonance states behaving as a single boson. It is therefore speculated that some of
these multi-meson resonances, when exchanged between two nucleons may
dominate the intermediate- and short-range behavior of the two-nucleon potential.
The potential computed in this way is called the one-boson-exchange potential
(OBEP). Besides the exchange of one π meson, also other exchanges have been
explicitly considered in the OBEP. A main difference amongst workers on the
meson theoretic two-nucleon potential lies in their manner of treatment of the two-
pion system. An approach in which the effect of the two-pion system is
parameterized through one or two isoscalar (T=0), scalar (J=0) mesons is one such
treatment. In another development of the theory, the effect of the S-state of the
two-pion system is parameterized through the scattering length and effective range.
In yet another attempt the effect of two-pion continuum is considered in more
detail and the resultant potential taken into account explicitly. Various authors also
differ in the details of their method of computing the potential. Broadly speaking,
conventional field-theoretical techniques and the dispersion theoretic method are
the two principal methods of solving the problem that we do not express these
methods in details here. Therefore, in other words, the boson exchange potentials
are based on effective field theory and are expanded to nucleon-nucleon, pion-
nucleon, and pion-pion interactions. These models do not any reference to QCD,
but the baryon and meson fields have been considered as the asymptotic states that
absorb all effects from quark-gluon dynamics. The discovery of the spin-one or
vector mesons ρ and ω with the masses around 770-780 MeV was provided a
progress and led to the expansion of the OBE potentials. In these models, the
unrelated single exchange contributions of the pseudoscalar mesons π (138) ,
(549) and the vector mesons (769), (783) as well as the scalar meson (983)
have been considered and iterated into the scattering equation. In addition, the two-
pion exchange associated with the fictional scalar sigma meson with the masses
around 400-800 MeV was demonstrated. The core region was finally
parameterized by the phenomenological form factors related to the meson-nucleon
vertices. Finally, those form factors formed the substructure of QCD. Such OBE
potentials provided the first quantitative approximation of data. Many models of
these potentials exist that each have owns definite and separable features. It is now
known that these are the standard NN potentials, of course. A few examples are
86
Nijmegen, Paris, and Bonn potentials. Broadly speaking, in this quark-antiquark
pair (=meson) exchange model, we have the following features:
a. It is similar to quark exchange (just reverse direction of one quark).
b. It gives a very good description of many aspects of NN potential.
c. It is preferred because meson states are color-neutral and have relatively low
mass (larger range).
d. It studies OPEP and generalizes to other mesons- so far only model that gives
perfect agreement with data, especially for long-range part.
5.3
5.3Basic
BasicPotentials
Potentials
The range of the nucleon-nucleon interaction is divided to the three parts: the
short-range (r 1 fm), the intermediate-range (1 fm r 2 fm), and the long
range (r 2 fm). For the long-range part, one-pion exchange (OPE) has usually
been considered. The short-range part has often been discussed
phenomenologically; in some models, form factors are introduced to regularize the
potential at the origin whereas in other models a hard core is used. The first logical
approach to describe the intermediate-range region was to include the two-pion
exchange (TPE) contributions. However, these TPE models, did not give a
satisfactory description of the NN scattering data, mainly due to a lack of a
sufficient spin-orbit force. Gammel, Christian, and Thaler hinted the necessity of a
spin-orbit force, when they tried to fit all of the data available at that time with a
phenomenological velocity dependent (local) potential as:
V =VC(r) +VT(r) S12
for each of four spin and isospin combinations and they failed. In 1975, the
simultaneous construction of the purely phenomenological potentials by Gammel-
Thaler and the semi-phenomenological Singell-Marshak potential, where both
models introduced phenomenological spin-orbit potentials, began. The Gammel-
Thaler model gave a good fit to scattering data up to 310 MeV. The Singell-
Marshak model, consisting of the TPE Gartenhaus potential together with a
phenomenological spin-orbit force, was successful up to 150 MeV. Okubo-
Marshak showed that the most general two nucleon potential, considering
symmetry conditions, is as follows:
87
V ( r, 1, 2 , 1 , 2 ) V0 ( r ) V ( r )( 1 . 2 ) V ( r )( 1. 2 ) V ( r )( 1. 2 )( 1. 2 )
+VLS ( r )( 1. 2 ) VLS ( r )( L.S )( 1. 2 )
VT ( r ) S12 VT ( r ) S12 ( 1. 2 )
VQ ( r )Q12 VQ ( r )Q12 ( 1 . 2 )
V pp ( 1 . p )( 2 . p ) V pp ( r )( 1. p )( 2 . p )( 1 . 2 )
where L, S, and Q12 are spin-orbit and quadratic spin-orbit- operators, respectively.
1
Q12 {( 1 .l )( 2 .l ) ( 2 .l )( 1 .l )}
2
Twelve terms are given by twelve radial functions V0(r) , ... . We can obtain the
V(r)'s from our knowledge from the basic nature of the nuclear force such as the
meson exchange and or from the semi-empirical procedure by fitting some
assumed forms of the radial dependence to experimental data. When our
understanding of QCD is fully developed in the future, it will be possible to
determine these functions from first principles. The first four terms are the central
force terms and in this case, L and S are the good quantum numbers. In the
presence of the other terms, two-nucleon system is invariant only in the combined
space of L and S labeled by J;
Vls ( r ) VLS (r ) L.S VLS ( L.S )(1 . 2 )
The reason for these two terms comes from the possibility that the radial
dependence of the isospin-dependent and of the isospin-independent parts may be
different from each other, for example as the result of different mesons being
exchanged. The six and the seven terms are the tensor force. The ninth and the
tenth quadratic spin-orbit terms enter only when there is momentum dependence in
the potential. The last two terms are often dropped since for elastic scattering, they
can be expressed as a linear combination of other terms. Their contributions
therefore cannot be determined using elastic scattering, for which most of our
information on NN interaction is derived. Then, soon after, better potential forms
were constructed. Some examples are Hamada-Johnston, Yale, and the various
hard- and soft-core models constructed by Reid. Before going into the treatment of
other potentials, it is useful to mention that most of the experimental elastic phase
shifts are extracted from the pp and np differential cross sections. In these models,
the data are fitted up to the energy range 0-350 MeV, because, as already
88
mentioned, in higher energies (with the threshold 270 MeV) the pion production
and other relativistic effects become important and the Schrödinger two-nucleon
equation is therefore no longer sufficient.
Hamada-Johnston and Yale group potentials reproduce all the two-body scattering
data (including the polarization parameters) as a function of energy over the energy
range of several hundred MeV. The Yale potential was especially designed to
reproduce the phase shifts in various two-nucleon states as smooth functions of
energy. As a first step, the phase parameters (phase shifts, and the mixing
parameter in the case of coupled states) were determined as a function of energy by
direct fit to all the scattering and polarization data. The setting up of the potential
with its parameters adjusted to reproduce the phase parameters may be regarded as
the second step in this type of work. The first step, namely the determination of the
phase parameters as a function of energy has been practiced very efficiently by
several groups of workers including the Yale, Livermore, and other- teams. The
actual procedure, now almost standardized, entails expressing the scattering
amplitude as the sum over partial waves up to a certain maximum orbital angular
momentum lmax (the usual value chosen for lmax is more or less 5). The contribution
of all higher partial waves is then taken to be represented by the one-pion exchange
contribution (OPEC) to the scattering amplitude. The Yale group took the OPEP as
a given component of the potential and then determined the rest of the potential by
fitting the energy-dependence phase parameters up to lmax.
5.4
5.4Hamada-Johnston
Hamada-JohnstonPotential
Potential
The Hamada-Johnston (HJ) potential is a leading phenomenological NN (pp+np
here) energy-independent potential. It described well the scattering data below 350
MeV and deuteron properties as well as the effective-range parameters. The
general form of HJ potential reads
V Vc ( r ) Vt ( r )S12 Vls ( r ) L.S Vll L12 ,
where
S12 3( 1 .r )( 2 .r ) ( 1 . 2 ),
L12 ( lj 1 . 2 ) L2 ( L.S ) 2
and
89
1
Vc (r ) 0.08( m pi )( 1. 2 )( 1. 2 )Y ( x )[1 acY ( x ) bcY 2 ( x )]
3
1 2
Vt ( r ) 0.08( m pi )( 1. 2 ) Z ( x )[1 atY ( x ) bY
t ( x )]
3
Vls (r ) m pi GlsY 2 ( x )[1 blsY ( x)]
Vll (r ) m pi Gll x 2 Z ( x )[1 allY ( x ) bllY 2 ( x )]
in which mpi, x and M are the pion mass (139.4 MeV), the inter nucleon distance
measured in the units of the pion Compton’s wavelength (r0 = 1.415 fm), and the
nucleon mass (taken to be 6.73µ), respectively. Note that
x = µr, µ = mpic/h = r −10
e x 3 3
Y ( x) , Z ( x) 1 2 Y ( x )
x x x
We should note that the quadratic spin-orbit potential was mainly introduced to
describe np data satisfactorily.
For the r large enough, Vc(r) and Vt(r) reduce to the well-known OPEP with the
pseudo vector coupling constant of 0.08.
The coefficients ac, bc, at and bt represent the potential diversion from OPEP at
small r’s.
Gls is the strength of the short ranged spin orbit potential Vls(r) and is depended
on the parity of state.
Gll, as the strength of Vll(r), originated from special evaluations, is determined
phenomenologically.
All the coefficients are determined from the detailed fit to scattering data.
The hard cores are considered for all states with their radius at xc = 0.343. The HJ
potential, as originally proposed, included a strong long-range quadratic spin-orbit
potential in triplet even states, and also a strong short-range spin-orbit potential in
triplet (l = j)-odd states, where it is known that the latter does not exist. So, the
potential for triplet-odd states was modified as follows: It was defined to be -
0.26744 mpi around xc < x 0.487 and by above standard relations for x > 0.487.
The values of the binding energy, electric quadratic moment, effective-range, D-
90
state probability and the asymptotic D-wave to S-wave ratio of deuteron were
determined by the potential to be 2.226 MeV, 0.285 fm2, 1.77 fm, 6.97 % and
AD/AS = 0.02656, respectively.
An improvement of HJ potential was made in (we call it Massachusetts-group
potential) to replace mainly the HJ hard cores (for x xc) by finite square-well
cores. Outside the square-well radius (for x > xc), the potential is the same as HJ
except for a few changes in parameters such as considering the pion mass
differences, and that the ac values of the singlet even and triplet-odd states as well
as the triplet-odd bc are changed slightly. The pion mass splitting leads to charge-
independent breaking (CIB) while CS is still preserved. Now, mpi is replaced by
the effective pion mass and xc = 0.4852, which in turn implies the larger coreradius
of 0.7 fm. Describing NN scattering data and deuteron properties with the potential
were good. Indeed, the main aim to form the latter potential was to show that the
hard cores were not necessary since all data could be described by the finite soft-
core potentials.
5.5
5.5Yale-Group
Yale-GroupPotential
Potential
The Yale-group potential is a pp+np phenomenological potential similar to HJ
potential that is fitted to its time phase parameters as well. There, an one pion
exchange potential (OPEP) is included directly and the quadratic spin-orbit
potential is considered in a somewhat different form than that of HJ. The whole
NN potential reads
V V (2)OPEP Vc ( r ) Vt ( r) S12 Vls (r ) L.S Vql [Q12 ( L.S ) 2 ],
[Q12 ( L.S )2 ] ( L.S ) 2 L.S L2
where
2
(2)
g 2pi 2
m pi 3 3 e x
V OPEP ( r )
12 m pi c ( 1 . 2 )[( 1. 2 ) S12 [1 x x 2 ] x
M
This OPEP is used for the distances larger than nearly 3fm, with the same
parameter definitions as in HJ potential. For the coupling constant, g2pi/14 = 0.94 is
used in singlet-even states and 1 elsewhere. For singlet-even and triplet-odd states,
the neutral-pion mass (mpi = m0 ) is used while for singlet-odd and triplet-even
91
states, a mean of the charged- and neutral-pion masses [mpi = (m0 + 2m±) /3] is
used. The hard-core radius is considered at xc = 0.35, and except in the OPEP part,
all the radial functions Vc, Vt, Vls and Vql are taken as
7
e 2 x
V an
n 1 xn
The potential’s parameters are determined by fitting to data for various states and
involved potentials. It is also notable that HJ and Yale potentials are OPEP for L >
5, and that the Yale potential sets Vls = 0 for J> 2.
5.6
5.6 Reid68
Reid68and
andReid-Day
Reid-DayPotentials
Potentials
Reid68 Potential
Among the failures of HJ and Yale hard-core potentials were that they could not
reproduce reasonable results when applying to many-body calculations. It appeared
that the Reid soft-core potentials were better.
The Reid potentials are static and local phenomenological potentials similar to
those of HJ and Yale. Reid determined the potential for each two-nucleon state
independent of the other states. So, one may suppose that this approach is
problematic in that, with many two-nucleon states each with its own potential,
fitting the experimental data could be probably meaningless. But, because the
highest energy in the analyses was about 350 MeV, just the two-nucleon states
with J 2, which are more important in nuclear calculations, were considered in
practice.
Reid used only a central potential in the singlet and uncoupled triplet-states while,
for the coupled triplet-states, he used
V Vc (r ) Vt (r ) S12 Vls ( r ) L.S
which has the central, tensor and usual spin-orbit components. For the LR part, he
used the OPEP of as a tail attached to the potential, with g2pi = 14, mpi = 138.13
MeV, M = 938.903 MeV and µ = 0.7fm−1. On the other hand, to remove the x−2 and
x-3 behaviors at small distances, an short range [SR] potential was subtracted from
the tensor part of the potential. For the medium range [MR’s], the potentials were
expressed as the sums of the Yukawa’s functions of e−nx/x, where n was an integer.
The SR repulsions were also some combinations of the severe hard-core and the
92
Yukawa soft-core potentials–It is mentionable that the criterion for a potential to
be soft-core is that the wave functions do not vanish in nonzero radiuses. For the
hard-core radius, when needed, the radiuses of xc 0.1 could be used there. One
should, of course, note that because of fitting the potentials to the energies often
below 350 MeV, finding a unique formalism for the SR part was almost difficult.
Finally, it is notable that the Reid potentials did not describe well some of the
scattering data and deuteron properties at that time. It was also hinted the need for
velocity-dependence and non locality in NN potentials, imposed by experimental
data.
Reid-Day Potential
The Reid68 soft-core potentials up to the higher partial waves to solve three-body
equation in nuclear matter calculations. In fact, he used three two-nucleon
potentials in calculations. The first one (called V2) was just the central part of the
Reid68 potential in 3S1 − 3D1 channel for all states. The second one (called
V6(Reid)) had four forms for the four (S,T) states. Indeed, in the latter case, for all
S = 0 states, just two central Vc(r) potentials (Reid68 1S0 and 1P1 for T = 1 and T =
0 respectively) were used; meanwhile for all S = 1 states, just two central Vc(r) and
two tensor Vt(r) potentials (Reid68 3P2 − 3F2 and 3S1 − 3D1 for T = 1 and T = 0
respectively) were used. The third one (called Full-Reid potential that we call
Reid-Day potential) used the original Reid68 potentials for all J 2 states;
meanwhile for the states with J 3, he set up the potentials based on the Reid68
ones almost roughly. Clearly, for the states up to J = 5, the potential structures
were similar to the original Reid68 ones. For example, in the coupled sate of 3D3 −
3G3, he used
Vc ( r ) 10.463Y ( x ) 103.4Y 2 ( x ) 419.6Y 4 ( x ) 9924.3Y 6 ( x )
12 3
Vt ( r ) 10.463 Z ( x ) 2 Y 4 ( x ) 351.77Y 4 ( x ) 1673.5Y 6 ( x )
x x
Vls ( r ) 650Y 4 ( x ) 5506Y 6 ( x )
where x = 0.7r, and r is the inter nucleon distance measured in fm as usual. For all
other not clearly mentioned states, he used the V6(Reid) potentials. Therefore, that
new expansion was not based on any fundamental underlying argument on NN
93
interaction, and was just to sake of applying the wanted potentials in some nuclear
calculations.
5.7Self
5.7 SelfLearning
LearningExercise
Exercise-I-I
Q.1 What is the extra term which included in Yale potential over HJ potential
Q.2 What is the physical significance of Compton wavelength?
Q.3 Write down the different range of nucleon-nucleon interaction.
Q.4 Write down the expression for HJ potential.
Q.5 What is the failure of HJ and Yale potential.
5.8
5.8One
OneBoson
BosonExchange
ExchangePotential
Potential
The nucleon-nucleon (NN) interaction has a complex structure as schematically
depicted in figure.
The central part of the nucleon-nucleon potential consists of a short range repulsive
part, an intermediate range attractive and a long range part. In modern relativistic
potentials based on field theory this interaction is described by the exchange of
various mesons which act as exchange bosons. The most important are the non-
strange mesons , , and . The total NN-interaction is given by the
superposition of the contributions from the various mesons. These contributions
are characterized by the coupling strength gi, the meson mass mi and the character
of the meson which determines the Lorentz structure of the meson nucleon vertex
i (scalar, vector, . . . ).
94
Coupling strength: gi with sign attractive +
repulsive –
Meson mass: mi determines the range
Meson-nucleon vertex: i determines the Lorentz structure
First of all we give a short overview of the different mesons and the corresponding
coupling properties:
-meson: m = 138 MeV, spin S=0, isospin I=1
pseudoscalar coupling where the tensor force is the most important part, long
range interaction
f
L NN ( x)i 5 ( x)u( x )
m
-meson: m≈ 550MeV , S=0, I=0
scalar coupling, attractive, intermediate range interaction
L NN g ( x ) ( x )
-meson: m = 783 MeV, S=1, I=0
vector coupling, repulsive, short range interaction
L NN g ( x ) ( x )
-meson: m = 770 MeV, S=1, I=1
vector and tensor coupling, short range interaction
g T
L NN g ( x ) ( x ) ( x ) ( x ) ( x) ( x)
2M
Mesons with isospin I = 1 are isovector particles and couple to the isospin of the
nucleon, i.e. they distinguish between protons and neutrons, mesons I = 0 are
isoscalar and do not distinguish. The -meson has a vector coupling and a tensor
coupling. The pion nucleon coupling strength f is determined by some fundamental
QCD relations (Effective chiral QCD Lagrangian). For all other mesons the
coupling strengths gi are fixed from empirical nucleon-nucleon scattering data.
Modern Boson-Exchange potentials describe NN-scattering data with high
95
precision. Such potentials were developed in the mid eighties. Typical examples
are the so-called Bonn and Nijmegen potentials developed by the Bonn-Julich and
the Nijmegen (Netherlands) research groups. In addition to the mesons discussed
above such potentials contain in addition an isoscalar pseudoscalar meson, the so-
called -meson, and an isovector scalar meson, the so-called -meson. Thus they
are based on a complete set of non-strange mesons (mesons which have no strange
quark content) with masses below 1 GeV. The model parameters, i.e. the meson-
nucleon coupling strengths (and additional parameters for form factors) are fitted
to NN-scattering data (about 3000 data points for proton-proton and proton-
neutron scattering).
Figure 2: Schematic representation of the one-boson exchange diagram.
Spin-structure of one-boson-exchange potentials
An expansion in 1/M to leading order yields the non-relativistic form of the scalar
and vector potentials.
1. Scalar potential, generated by the -meson
g s2 e msr g s2 1 d e ms r
Vs ( r ) L.S
4 r 4 2 M 2 r 2 dr r
where S = 1/2 (1 + 2) is the total spin and L the total angular momentum of
the two-nucleon system.
2. Vector potential, represented by - and -mesons
gV2 e mv r g v2 gT 1 d gT
VV ( r ) 3 4 2 2 3 4 L.S
4 r 4 gv 2 M r dr gv
2
g2 gT mV2 e mV r
+ v 1 ( 1 )( 2 )
4 g v 4 r
96
Momentum space representation of the OBE potentials
We want now first to evaluate the Feynman-diagram which corresponds to a one-
meson exchange. For the moment we disregard the isospin. In the two-nucleon
center-of-mass system the incoming nucleons have momenta ±q, the outgoing
nucleons have momenta ±q ′. The nucleons are on-shell and therefore we have
E M 2 q2
E ' M 2 q '2
Since we consider only elastic scattering, energy-momentum conservation implies
| q ' || q |
E E'
Applying the Feynman rules for evaluating the meson exchange potential V(q,q′)
where the index stands for the various types of possible mesons exchanged
= , , , · · · , one finds
V g1u1 ( q ')1u1 ( q) D ( q q ') g2 u2 ( q ')2 u2 (q)
D represents the meson propagator. The meson propagator is different for
(pseudo)-scalar and vector particles and reads
P
D
( q q ') 2 m2
where P depends on the type of interchanged meson:
1 (pseudo) scalar meson: ,
P v
g vector meson: ,
The 1,2 matrices are the so-called vertex-functions or meson-nucleon couplings
which are given by
Particle : − meson Pion − meson
: 1 5 .
We now give a basic example to illustrate our findings. Consider the case that a
scalar meson () is exchanged. This is the simplest example, but the other
97
amplitudes can be evaluated in an analogous way. We discuss elastic, i.e. on-shell
scattering with
E = E′.
In this case V becomes
u1 ( q ')u1 ( q)u2 ( q ')u2 ( q)
V ( q) g2
( q ' q) 2 m2
To compute V, we use
u1 (q)u1 q u1† (q) 0 u1 q
1
( E ' M )( E M ) .q '
= 1, .q '
4 EE ' E ' M
E ' M
E M q '.q i 1 .( q ' q)
= 1
2 E ( E M )2
and we insert following relation
( .a)( ·b) = a ·b + i · (a ×b) .
Now we introduce the momentum transfer
k ≡ q ′− q
and the center-of-mass momentum
P =1/2(q + q ′)
The vector product reads in terms of c.m. momentum and momentum transfer
n = q × q′ ≡ P ×k .
Furthermore, in the nonrelativistic limit with E M, one obtains
q2
E M 2 q 2 M (1 ...)
2M 2
The total matrix element for the scalar exchange contains two vertices of type
ūu and the meson propagator. The latter is taken in its static form (−1)/(k2 + m2).
Altogether, this yields in the non-relativistic limit, the scalar potential of form
98
1
g 2
( 1 2 )( i ) k P
V ( k ) 2
1 2
k m2 2M 2
We recognize an attractive Yukawa potential and the spin-orbit potential which is
the second term in brackets. It corresponds to O4 of the complete operator
expansion given below.
The complete OBE potentials as e.g. the Bonn potentials can be reduced to a
nonrelativistic representation by expanding the full field-theoretical OBE Feynman
amplitudes into a set of spin and isospin operators
V [Vi V 'i 1. 2 ]Oi
i
The operators Oi obtained in this low energy expansion, assuming identical particle
scattering and charge independence, are defined as
O1 1
O2 1 . 2
O3 ( 1.k )( 2 .k )
i
O4 ( 1 2 ).n
2
O5 ( 1.n )( 2 .n)
Where
k =q −q,
n = q × q ≡P × k
and P = 1/ 2 (q + q ) is the average momentum.
The potential forms Vi are then functions of k, P, n and the energy. In order to
perform a non-relativistic reduction, usually the energy E is expanded in k2 and P2
E(q) =(k2/4 + P2 + M2 )1/2 ≃ M + k2 /8M + P2/2M
and terms to leading order in k2 /M2 and P2 /M2 are taken into account. The meson
propagators D(k2 ) are approximated by their static form (−1)/(k2+m2 ).
99
O1 1
O2 1. 2
O3 S12 3( 1 .r )( 2 .r ) 1. 2
O4 L.S
1
O5 Q12 [( 1.L )( 2 .L) ( 2 .L)( 1.L)]
2
These operators are the well known central, spin-spin, tensor, spin-orbit and
quadratic spin-orbit operators, respectively. The total angular momentum is
denoted by L = r × P and the total spin S = 1/ 2 (1 +2).
5.9
5.9Self
SelfLearning
LearningExercise-II
Exercise-II
Q.1 Draw the schematic diagram of nucleon-nucleon (NN) interaction.
Q.2 Give a short overview of different mesons and corresponding coupling
properties.
Q.3 Explain the momentum space representation of the OBE potential.
5.10
5.10Summary
Summary
In this chapter we discussed various types of nuclear potentials. This chapter
started with the introduction of nuclear potentials and followed by HJ, Reid and
OBEP.
5.11
5.11Glossary
Glossary
Nuclear force: The force that holds the nucleus together. Originally thought to be
the exchange of pions, as suggested by Yukawa. Pions are now known to not be
elementary themselves, but quarks which are held together by gluons.
Boson: A particle having spin that is an integer multiple of .
Meson: A particle (such as the pion) made of quark-antiquark pairs.
Interaction :Influence of a physical body on another body or the coupling between
a field and its source. Interactions can be of the most diverse types, e.g.
gravitational interaction, electromagnetic interaction, weak interaction, strong
interaction.
100
5.12
5.12Answers
AnswerstotoSelf
SelfLearning
LearningExercises
Exercises
Answers to Self Learning Exercise-I
Ans.1: OPEP
Ans.2: Compton wavelength is kind of the quantum mechanical cutoff - the length
scale below which quantum mechanics can not be simply ignored in favor of
classical approximations.
Ans.3: Range of the nucleon-nucleon interaction is divided to the three parts: the
short-range (r 1fm), the intermediate-range (1fm r 2fm), and the long
range (r 2fm).
Ans.4: Section 5.4
Ans.5: Failure of HJ and Yale hard-core potentials were that they could not
reproduce reasonable results when applying to many-body calculations.
Answers to Self Learning Exercise-II
Ans.1,2,3: See Section 5.7
5.13
5.13Exercise
Exercise
Q.1 Write down the expression for OPEP.
Q.2 Write a short note on
OBEP
Hamada-Johnston Potential
Reid potential
References
Referencesand
andSuggested
SuggestedReadings
Readings
1. Advances in Nuclear Physics By Michel Baranger, Erich Vogt, 2012
2. Concepts of Nuclear Physics By Bernard Leonard Cohen, 1971.
3. The Nucleon-nucleon Interaction and the Nuclear Many-body Problem by
Gerald E. Brown and T.T.S. Kuo 2010
101
UNIT-6
Interaction of Radiation and
Charged Particle with Matter
Structure of the Unit
6.0 Objectives
6.1 Introduction
6.2 Law of absorption and attenuation coefficient
6.3 Interaction processes
6.4 Target and projectile dependence of all three processes
6.5 Self learning exercise- I
6.6 Interactions of charged particles with matter
6.7 Energy loss of charged particles due to ionization
6.8 Bremstrahlung
6.9 Self learning exercise II
6.10 Summary
6.11 Glossary
6.12 Answers to self learning exercises
6.13 Exercise
References and Suggested Readings
6.0
6.0Objectives
Objectives
From this chapter student should develop their understanding of the various ways
photons, charged particles and neutrons can interact with matter and the concepts,
such as mass attenuation coefficient, stopping power and range, that have been
invented in order to aid that understanding. These ideas are the basis for the later
study of the effects of x rays, gamma radiation and other ionizing radiations on
living things.
102
6.1
6.1Introduction
Introduction
Gamma-rays, x-rays, neutrons, and neutrinos all have no net charge - they are
electro-statically neutral. In order to detect them they must interact with matter and
produce an energetic charged particle. In the case of gamma and x-rays, a photo-
electron is produced. In the case of neutrons, a proton is given kinetic energy in a
billiard ball like collision.
Knowledge of gamma-ray interactions is important to the Non Destructive
Assayist(NDA) in order to understand gamma-ray detection and attenuation. A
gamma ray must interact with a detector in order to be “seen.” Although the major
isotopes of uranium and plutonium emit gamma rays at fixed energies and rates,
the gamma-ray intensity measured outside a sample is always attenuated because
of gamma-ray interactions with the sample. This attenuation must be carefully
considered when using gamma-ray NDA instruments. This chapter discusses the
exponential attenuation of gamma rays in bulk materials and describes the major
gamma-ray interactions, gamma-ray shielding, filtering, and collimation. The
treatment given here is necessarily brief.
6.2
6.2Law
LawofofAbsorption
Absorptionand
andAttenuation
AttenuationCoefficient
Coefficient
Gamma rays were first identified in 1900 by Becquerel and Villard as a component
of the radiation from uranium and radium that had much higher penetrability than
alpha and beta particles. In 1909, Soddy and Russell found that gamma-ray
attenuation followed an exponential law and that the ratio of the attenuation
coefficient to the density of the attenuating material was nearly constant for all
materials
Law of Gamma-Ray Attenuation
Figure1
103
Figure1 illustrates a simple attenuation experiment. When gamma radiation of
intensity I0 is incident on an absorber of thickness L, the emerging intensity (I)
transmitted by the absorber is given by the exponential expression
I I 0 e l L
where l is the attenuation coefficient (expressed in cm–1). The ratio I/I0 is called
the gamma-ray transmission.
Figure 2
Figure illustrates exponential attenuation for three different gamma-ray energies
and shows that the transmission increases with increasing gamma-ray energy and
decreases with increasing absorber thickness. Measurements with different sources
and absorbers show that the attenuation coefficient l depends on the gamma-ray
energy and the atomic number (Z) and density () of the absorber. The reciprocal
of the attenuation coefficient 1/l has units of length and is often called the mean
free path. The mean free path is the average distance a gamma ray travels in the
absorber before interacting; it is also the absorber thickness that produces a
transmission of l/e, or 0.37.
104
Mass Attenuation Coefficient
The linear attenuation coefficient is the simplest absorption coefficient to measure
experimentally, but it is not usually tabulated because of its dependence on the
density of the absorbing material. For example, at a given energy, the linear
attenuation coefficients of water, ice, and steam are all different, even though the
same material is involved.
Gamma rays interact primarily with atomic electrons; therefore, the attenuation
coefficient must be proportional to the electron density P, which is proportional to
the bulk density of the absorbing material. However, for a given material the ratio
of the electron density to the bulk density is a constant, Z/A, independent of bulk
density. The ratio Z/A is nearly constant for all except the heaviest elements and
hydrogen.
P= Z / A
where
P = electron density
Z = atomic number
= mass density
A = atomic mass.
The ratio of the linear attenuation coefficient to the density (l/) is called the
mass attenuation coefficient and has the dimensions of area per unit mass
(cm2/gm). The units of this coefficient hint that one may think of it as the effective
cross-sectional area of electrons per unit mass of absorber. The mass attenuation
coefficient can be written in terms of a reaction cross section, (cm2):
N 0
A
where N0 is Avagadro’s number (6.02 x 1023) and A is the atomic weight of the
absorber. The cross section is the probability of a gamma ray interacting with a
single atom. The mass attenuation coefficient, can be rewritten as
I I 0 e L I 0 e x
x L
105
cm 2
where x mass thickness
gm
6.3
6.3Interaction
InteractionProcesses
Processes
The gamma rays interact with detectors and absorbers by three major processes:
photoelectric absorption, Compton scattering, and pair production and fall in the
range 10 to 2000 keV and. In the photoelectric absorption process, the gamma ray
loses all of its energy in one interaction. The probability for this process depends
very strongly on gamma-ray energy E and atomic number Z. In Compton
scattering, the gamma ray loses only part of its energy in one interaction. The
probability for this process is weakly dependent on E and Z. The gamma ray can
lose all of its energy in one pair-production interaction. However, this process is
relatively unimportant for fissile material assay since it has a threshold above 1
MeV.
Photoelectric Absorption
A gamma ray may interact with a bound atomic, electron in such a way that it loses
all of its energy and ceases to exist as a gamma ray (Figure3).
Figure 3
Some of the gamma-ray energy is used to overcome the electron binding energy,
and most of the remainder is transferred to the free electron as kinetic energy. A
very small amount of recoil energy remains with the atom to conserve momentum.
This is called photoelectric absorption because it is the gamma-ray analog of the
process discovered by Hertz in 1887 whereby photons of visible light liberate
electrons from a metal surface. Photoelectric absorption is important for gamma-
106
ray detection because the gamma ray gives up all its energy, and the resulting pulse
falls in the full-energy peak.
The probability of photoelectric absorption depends on the gamma-ray energy, the
electron binding energy, and the atomic number of the atom. The probability is
greater the more tightly bound the electron; therefore, K electrons are most
affected (over
80% of the interactions involve K electrons), provided the gamma-ray energy
exceeds the K-electron binding energy. The probability is given approximately by
Equation,
Z 4 / E3
which shows that the interaction is more important for heavy atoms like lead and
uranium and low-energy gamma rays:
where = photoelectric, mass attenuation coefficient.
This proportionality is only approximate because the exponent of Z varies in the
range 4.0 to 4.8. As the gamma-ray energy decreases, the probability of
photoelectric absorption increases rapidly. Photoelectric absorption is the
predominant interaction for low-energy gamma rays, x rays, and bremsstrahlung.
The energy of the photoelectron Ee released by the interaction is the difference
between the gamma-ray energy E and the electron binding energy Eb:
Ee E Eb
In most detectors, the photoelectron is stopped quickly in the active volume of the
detector, which emits a small output pulse whose amplitude is proportional to the
energy deposited by the photoelectron. The electron binding energy is not lost but
appears as characteristic x rays emitted in coincidence with the photoelectron. In
most cases, these x rays are absorbed in the detector in coincidence with the
photoelectron and the resulting output pulse is proportional to the total energy of
the incident gamma ray. For low-energy gamma rays in very small detectors, a
sufficient number of K x rays can escape from the detector to cause escape peaks
in the observed spectrum; the peaks appear below the full-energy peak by an
amount equal to the energy of the x ray.
107
Figure 4
Figure shows the photoelectric mass attenuation coefficient of lead. The interaction
probability increases rapidly as energy decreases, but then becomes much smaller
at a gamma ray energy just below the binding energy of the K electron. This
discontinuity is called the K edge below this energy the gamma ray does not have
sufficient energy to dislodge a K electron. Below the K edge the interaction
probability increases again until the energy drops below the binding energies of the
L electron; these discontinuities are called the LI, LII, and LIII edges. The presence
of these absorption edges is important for densitometry and x-ray fluorescence
measurements.
Compton Scattering
Compton scattering is the process whereby a gamma ray interacts with a free or
weakly bound electron (E >> Eb) and transfers part of its energy to the electron
(Figure5).
108
Figure 5
Conservation of energy and momentum allows only a partial energy transfer when
the electron is not bound tightly enough for the atom to absorb recoil energy. This
interaction involves the outer, least tightly bound electrons in the scattering atom.
The electron becomes a free electron with kinetic energy equal to the difference of
the energy lost by the gamma ray and the electron binding energy. Because the
electron binding energy is very small compared to the gamma-ray energy, the
kinetic energy of the electron is very nearly equal to the energy lost by the gamma
ray:
Ee= E– E’
where Ee = energy of scattered electron
E = energy of incident gamma ray
E’ = energy of scattered gamma ray.
Two particles leave the interaction site: the free electron and the scattered gamma
ray. The directions of the electron and the scattered gamma ray depend on the
amount of energy transferred to the electron during the interaction.
E ' m0 c 2 / (1 cos m0 c 2 / E )
Equation gives the energy of the scattered gamma ray.
Where m0c2 = rest energy of electron = 511 keV
= angle between incident and scattered gamma rays.
This energy is minimum for a head-on collision where the gamma ray is scattered
180°and the electron moves forward in the direction of the incident gamma ray.
For this case the energy of the scattered gamma ray is given by
109
E '(min) m0 c 2 / (2 m0 c 2 / E ) m0 c 2 / 2 256keV ;
E m0 c 2 / 2
and the energy of the scattered electron is given by
Ee (max) E / (1 m0 c 2 / 2 E ) E m0 c 2 / 2 E 256keV ;
E m0 c 2 / 2
For very small angle scatterings ( 0), the energy of the, scattered gamma ray is
only slightly less than the energy of the incident gamma ray and the scattered
electron takes very little energy away from the interaction. The energy given to the
scattered electron ranges from near zero to the maximum given by above equation.
Pair Production
A gamma ray with an energy of at least 1.022 MeV can create an electron-positron
pair when it is under the influence of the strong electromagnetic field in the
vicinity of a nucleus (Figure).
Figure 6
In this interaction the nucleus receives a very small amount of recoil energy to
conserve momentum, but the nucleus is otherwise unchanged and the gamma ray
disappears. This interaction has a threshold of 1.022 MeV because that is the
minimum energy required to create the electron and positron. If the gamma ray
energy exceeds 1.022 MeV, the excess energy is shared between the electron and
positron as kinetic energy. This interaction process is relatively unimportant for
nuclear material assay because most important gamma-ray signatures are below
1.022 MeV.
The electron and positron from pair production are rapidly slowed down in the
absorber. After losing its kinetic energy, the positron combines with an electron in
110
an annihilation process; which releases two gamma rays with energies of 0.511
MeV. These lower energy gamma rays may interact further with the absorbing
material or may escape. In a gamma-ray detector, this interaction often gives three
peaks for a high-energy gamma ray. The kinetic energy of the electron and
positron is absorbed in the detector. One or both of the annihilation gamma rays
may escape from the detector or they may both be absorbed. If both annihilation
gamma rays are absorbed in the detector, the interaction contributes to the full-
energy peak in the measured spectrum; if one of the annihilation gamma rays
escapes from the detector, the interaction contributes to the single-escape peak
located 0.511 MeV below the full-energy peak; if both gamma rays escape, the
interaction contributes to the double-escape peak located 1.022 MeV below the
full-energy peak. The relative heights of the three peaks, depend on the energy of
the incident gamma ray and the size of the detector. ‘These escape peaks may arise
when samples of irradiated fuel, thorium, and 232Uare measured because these
materials have important gamma rays above the pair-production threshold.
6.4
6.4Target
Targetand
andProjectile
ProjectileDependence
Dependenceofofallallthree
threeProcesses
Processes
The relative importance of the three main interaction mechanisms depends on the
energy of the incident photon and the nature of the absorbing material. In general
terms the photoelectric effect is most important at low energies. At higher energies
Compton scattering becomes the main energy loss mechanism. At still higher
photon energies Compton scattering is less effective. Above 1.1 MeV pair
production becomes possible and is the dominant effect for energies greater than a
few MeV. We can specify the energies at which relative importance of the effects
changes by defining the energy at which they have the same value of the mass
attenuation coefficient, µm.
Let E(pe,C) be the energy at which an incident photon loses energy at the same
rate by both the photoelectric (pe) and Compton (C) effects. Its value is given by
the point at which the photoelectric and Compton curves cross on the graph of
attenuation coefficient and energy (Figure7).
Similarly E(C,pp) is the energy at which an incident photon loses energy at the
same rate by both Compton scattering and by pair production (pp). The values of
these changeover energies depend on the nature of the material; both E(pe,C) and
111
E(C,pp) vary with the atomic number, Z, of the absorbing material, as shown in
figure.8
Figure:7
Figure:8
The total mass attenuation coefficient is just the sum of all the contributions from
the different processes
µm[tot] = µm[pe] + µm[C] + µm[pp]
This total mass attenuation coefficient describes the decrease of the original
incident radiation. The total linear attenuation coefficient is given by
112
µl [tot] = µm[tot] .
Compton scattering produces a photon of reduced energy which nevertheless may
interact again. Similarly the electrons and positrons produced in pair production
may have large energies which they carry with them deeper into the material.
Hence the exponential decrease law using the mass attenuation coefficient
underestimates the total amount of radiation energy penetrating materials.
6.5Self
6.5 SelfLearning
LearningExercise-I
Exercise-I
Q.1 Which process of attenuation is dominant for 10 MeV photons?
Q.2 Write down the law of absorption.
Q.3 The mass attenuation coefficients for photons in lead are shown in the
accompanying diagram. Label the curves according to the process they
represent.
Figure:9
Q.4 Pair production by photons has two restrictions. The first is that the energy
of the photons must be greater than 1.02 MeV and the second is that pair
production can occur only near a heavy charged particle. Explain the
reasons behind these restrictions.
6.6
6.6Interactions
InteractionsofofCharged
ChargedParticles
Particleswith
withMatter
Matter
Charged particles, such as electrons, protons and alpha particles, interact with
matter electromagnetically or through one of the two kinds of nuclear interactions,
113
the weak interaction or the strong interaction. The electromagnetic interaction
involving collisions with electrons in the absorbing material is by far the most
common. Neutral particles such as the neutron can interact only through the
nuclear interactions. Thus charged particles can be detected directly by their
electromagnetic interactions whereas neutral particles have to suffer nuclear
interactions which produce charged particles before their presence can be detected.
Electromagnetic interactions:
The electromagnetic interaction consists mainly of two mechanisms: (a) excitation
and ionization of atoms, and (b) bremsstrahlung, the emission of electromagnetic
radiation (photons) when a charged particle is severely accelerated, usually by
interaction with a nucleus. A third kind of interaction, producing Cherenkov
radiation, while playing an important role in the detection of very high energy
charged particles, absorbs only a small amount of energy. The contribution of each
mechanism depends on the charge, mass and speed of the incident particle as well
as the atomic numbers of the elements which make up the absorbing material.
Individual interactions – scattering:
Unlike photons, each charged particle suffers many interactions along its path
before it finally comes to rest, but only a small fraction of its energy is lost at each
interaction. For example, a typical alpha particle might make fifty thousand
collisions before it stops. Hence the energy loss can usually be considered as a
continuous process. Charged particles are deflected or scattered at each interaction.
Although the amount of scattering at each collision may be small, the cumulative
effect may be quite a large change in the direction of travel. Occasionally an
incident particle will pass very near a nucleus and then there will be a single large
deflection. This nuclear scattering effect is most pronounced for light incident
particles interacting with heavy target nuclei.
Stopping power:
There are several ways of describing the net effects of charged-particle
interactions, the rate of energy loss along the particle's path, -dE/dx , being most
important. Here E is the particle's energy and x is the distance travelled. This rate
of energy loss with distance travelled depends on the material and is called the
linear stopping power, Sl, of the material:
114
dE
Sl
dx
A common unit for linear stopping power is MeV.m-1. In general the stopping
power will vary as the particle loses energy so it depends on the charged particle's
energy. The linear stopping power of a material also depends on the density of
electrons within the material (and hence on the atomic numbers of the atoms) as
well as the energy of the particle. So a more fundamental way of describing the
rate of energy loss is to specify the rate in terms of the density thickness, rather
than the geometrical length of the path. So energy loss rates are often given as the
quantity called the mass stopping power:
dE 1 dE
Sl
d ( x) dx
where is the density of the material and x is the density-thickness.
6.7
6.7Energy
EnergyLoss
LossofofCharged
ChargedParticles
Particlesdue
duetotoIonization
Ionization
The dominant mechanism of energy loss at lower (non-relativistic) energies is the
electromagnetic interaction between the moving charged particle and atoms within
the absorbing material. Since the electromagnetic interaction extends over some
distance, it is not necessary for the charged particle to make a direct collision with
an atom; it can transfer energy simply by passing close by. However, since the
internal energy of an atom is quantized, only certain restricted values of energy can
be transferred. The incident particle can transfer energy to the atom, raising it to a
higher energy level (excitation) or it may transfer enough energy to remove an
electron from the atom altogether (ionisation). Although this fundamental
mechanism operates for all kinds of charged particles, there are considerable
differences in the overall patterns of energy loss and scattering between the
passage of light particles (electrons and positrons), heavy particles (muons,
protons, alpha particles and light nuclei), and heavy ions (partially or fully ionised
atoms of high Z elements). Most of these differences arise from the dynamics of
the collision process. In general, when a massive particle collides with a much
lighter particle, the laws of energy and momentum conservation predict that only a
small fraction of the massive particle's energy can be transferred to the less
massive particle. The actual amount of energy transferred will depend on how
115
closely the particles approach and restrictions imposed by quantization of energy
levels. The largest energy transfers occur in head-on collisions.
In non-relativistic newtonian dynamics, when an object A (mass M) hits a
stationary object B (mass m) head-on the laws of dynamics predict that the energy
lost by the incident particle is
mM
K B 4K A 2
M m
where KA is the kinetic energy of the incident particle. For the case M >> m this
becomes
m
K B 4K A
M
The energy transferred is a very small fraction of the incident particle's energy.
However when M = m then all the kinetic energy is transferred to the target (KB =
KA) and the projectile stops. This result is strictly true only for particles travelling
with speeds much less than that of light (non-relativistic speeds) but similar results
are obtained also for relativistic particle speeds. When the collision is not head-on
the energy transfer to the target is less and of course the energy loss of the incident
particle is correspondingly less as well.
Energy loss by heavy particles:
When a massive particle collides with an electron the energy lost at each collision
is relatively small. For example, a slow alpha particle hitting an electron transfers a
maximum of only 0.05% of its energy to the electron. Since head-on collisions are
rare, usually the energy loss is much lower. Many collisions are needed to
significantly reduce the incident particle's energy. Therefore we can consider the
energy loss as a continuous process. Although the energy given to an electron may
be a small fraction of the incident energy, it may be sufficient to ionize the atom
and for the ejected electron to travel some distance away from the interaction
point, leaving a trail of excited and ionized atoms of its own. These 'knock-on'
electrons can leave tracks called delta rays. Mostly, however, the knock-on
electrons will lose their energy within a very short distance of the interaction point.
The energy dependence of the rate of energy loss (stopping power) by excitation
and ionization of heavy particles for some typical materials is shown in figure.
116
This graph is a plot of the energy-loss rate as a function of the kinetic energy of the
incident particle.
Figure:10
Note that the stopping power is expressed using density-thickness units. To obtain
the energy loss per path length you would need to multiply the energy loss per
density-thickness (shown on the graph) by the density of the material. As for
photon
interaction, it is found that when expressed as loss rate per density-thickness, the
graph is nearly the same for most materials. There is, however, a small systematic
variation; the energy loss is slightly lower in materials with larger atomic numbers.
The diagram shows the rate of energy loss for the extreme cases of carbon (Z = 6)
and lead (Z = 82). At high incident energies there is also some variation with
density of the same material because a higher density of atomic electrons protects
the more distant electrons from interactions with the incident particle. This results
in lower energy loss rates for higher densities.
For low energies the stopping power varies approximately as the reciprocal of the
particle's kinetic energy. The rate of energy loss reaches a minimum, the minimum
ionization point, and then starts to increase slowly with further increases in kinetic
energy. Minimum ionization occurs when the particle's kinetic energy is about 2.5
times its rest energy, and its speed is about 96% of the speed of light in vacuum.
Although the energy loss rate depends only on the charge and speed of the incident
particle but not on its mass it is convenient to use kinetic energy and mass rather
117
than the speed. At minimum ionization the energy loss is about 0.2 MeV.(kg.m−2)−1
(= 3 × 10−12 J.m2.kg−1 in SI units), decreasing slightly with increasing atomic
number of the absorbing material. The distance that a particle penetrates a material
before it loses all its kinetic energy is called the range of that particle. Energy loss
along the path is shown in figure11.
Figure:11
The rise near the end of the path is due to the increased energy loss rate at low
incident energies. At very low speeds the incident particle picks up charge from the
material, becomes neutral and is absorbed by the material.
For a given material the range will be the nearly the same for all particles of the
same kind with the same initial energy. The number of particles as a function of
distance along the path is shown in figure12.
Figure 33: Range and straggling
A small variation in the range, called straggling, is due to the statistical nature of
the energy loss process which consists of a large number of individual collisions.
118
The actual number of collisions is always subject to some fluctuation. In spite of
that, the average range can be used to determine the average energy of the incident
particles.
Energy loss by electrons and positrons:
Electrons and positrons also lose energy by ionization but there are several
differences. There is a slight difference between the interactions of positrons and
electrons, resulting in a slightly higher energy loss for the positrons. Both,
however, have lower loss rates at high energies than heavier particles travelling at
the same speed. Because of its light mass an electron is easily scattered in
collisions with other electrons. The resulting erratic path will be longer than the
linear penetration (range) into the material and there will be greater straggling.
6.8
6.8Bremsstrahlung
Bremsstrahlung
The name bremsstrahlung comes from the German; the literal translation is
'braking radiation'. It occurs when a charged particle is accelerated - that is
whenever its speed or direction of motion changes. The effect is most noticeable
when the incident particle is accelerated strongly by the electric field of a nucleus
in the absorbing material. An accelerated charged particle radiates electromagnetic
energy (photons). Since the effect is much stronger for lighter particles, it is much
more important for beta particles (electrons and positrons) than for protons, alpha
particles, and heavier nuclei. At particle energies below about 1 MeV the energy
loss due to radiation is very small and can be neglected. Radiation loss starts to
become important only at particle energies well above the minimum ionization
energy. At relativistic energies the ratio of loss rate by radiation to loss rate by
ionization is approximately proportional to the product of the particle's kinetic
energy and the atomic number of the absorber. So the ratio of stopping powers is
Sl [rad ] 1
ZE
Sm [coll ] E '
where E is the particle's kinetic energy, Z is the mean atomic number of the
absorber and E' is a proportionality constant; E' ≈ 800 MeV.
The kinetic energy at which energy loss by radiation equals the energy loss by
collisions is called the critical energy, Ec. Approximately
119
E ' 800 MeV
Ec
Z Z
Another quantity of interest is the radiation length, defined as the distance over
which the incident particle's energy is reduced by a factor e-1(0.37) due to radiation
losses alone. Some typical values are given in table.
Material Critical energy Radiation Density×
Ec / MeV length radiation length
L/m L / kg.m-2
Air 102 200 362
Water 92 0.36 361
Aluminium 51 0.089 240
Iron 27 0.018 140
Lead 9.5 0.0056 64
Bremsstrahlung by a high energy electron results in a high energy photon as well
as a high energy electron. Pair production by high energy photons results in a high
energy electron and a high energy positron. In both cases two high energy particles
are produced from a single incident particle. Furthermore the products of one of
these processes can be the incident particles for the other. The result can be a
cascade of particles which increases in number, while decreasing in energy per
particle, until the average kinetic energy of the electrons falls below the critical
energy. The cascade is then absorbed by ionization losses. Such cascades, or
showers, can penetrate large depths of material.
6.9
6.9Self
SelfLearning
LearningExercise II
Exercise-II
Q.1 Define linear stopping power.
Q.2 Draw a ‘Range and straggling curve’.
Q.3 Explain the phenomena behind the energy loss of charged particles due to
ionization.
Q.4 Explain why "bremsstrahlung" is a more important energy loss mechanism
for electrons than for protons travelling through matter.
120
6.10
6.10Summary
Summary
In this chapter we discussed various interaction phenomena of radiation and
charged particle with matter. This chapter started with the introduction of law of
absorption and attenuation coefficient followed by photon interaction with matter
via Photoelectric effect, Compton scattering and pair production. After that we also
discussed the interaction of charged particles with matter. At last we also discussed
the Bremstrahlung energy which is nothing but the 'braking radiation'.
6.11
6.11Glossary
Glossary
Electromagnetic radiation: Radiation consisting of electric and magnetic waves
that travel at the speed of light. Examples: light, radio waves, gamma rays, x-rays.
Gamma ray : A highly penetrating type of nuclear radiation, similar to x-
radiation, except that it comes from within the nucleus of an atom, and, in general,
has a shorter wavelength.
Ionizing radiation:Radiation that is capable of producing ions either directly or
indirectly.
Scattering:A process that changes a particle's trajectory. Scattering is caused by
particle collisions with atoms, nuclei and other particles or by interactions with
electric or magnetic fields. If there is no change in the total kinetic energy of the
system, the process is called elastic scattering. If the total kinetic energy changes
due to a change in internal energy, the process is called inelastic scattering.
6.12
6.12Answers
AnswerstotoSelf
SelfLearning
LearningExercises
Exercises
Answers to Self Learning Exercise- I
Ans.1: Pair production
Ans.2: See Section 6.2
Ans.3,4:See Section 6.3
Answers to Self Learning Exercise- II
Ans.1: The rate of energy loss with distance travelled depends on the material and
is called the linear stopping power, Sl, of the material
dE
Sl
dx
121
A common unit for linear stopping power is MeV.m-1.
Ans.2,3: See Section 6.7
Ans.4: See Section 6.8
6.13Exercise
6.13 Exercise
Q.1 Define straggling.
Q.2 Explain why energy loss rate by "Bremsstrahlung" is greater for electrons
travelling through lead than for electrons travelling through water.
Q.3 Write a short note on
1. Photoelectric effect
2. Pair production
3. Compton effect
References
Referencesand
andSuggested
SuggestedReadings
Readings
1. The Atomic Nucleus by R. D. Evans, 1955.
2. Radiation Detection and Measurement by G. F. Knoll, 1979.
3. Elementary Nuclear Theory by Bethe and Morrison.
4. Nuclear Physics by D. C Tayal.
5. Nuclear Physics by Irving Kaplan.
6. Introductory Nuclear Physics by Kenneth S. Krane
7. R.R. Roy and B.P. Nigam: Nuclear Physics, 1979.
122
UNIT-7
Detectors
Detectors-I
Structure of the Unit
7.0 Objectives
7.1 Introduction
7.2 Ionization Methods for Measurement of Radiation
7.3 Ionization chamber
7.4 Proportional Counters
7.5 Geiger-Muller Counter (GM Counter)
7.6 Self learning exercise -I
7.7 Scintillation Counter
7.8 Self learning exercise -II
7.9 Answers to self learning exercises
7.10 Exercise
7.11 Summary
7.12 Glossary
References and Suggested Readings
7.0
7.0Objectives
Objectives
After going through this lesson, you would be able to understand
1. some of the most useful procedures for the detection and measurement of
radiations like Alpha & Beta particles.
2. the way in which the measurements of radiations are carried out.
7.1
7.1Introduction
Introduction
Experiments in Nuclear and Particle Physics depend upon the detection of primary
radiation/particle and that of the product particles if any. The detection is made
123
possible by the interaction of nuclear radiation with atomic electrons directly or
indirectly.
The same detector may be used to study different types of radiation according to
different phenomena. Thus, G.M. counters register all sorts of charged particles
through ionization effects. Scintillation counters detect gamma rays by
photoelectric effect, Compton scattering or pair production depending on gamma
ray energy.
The detection efficiency of an instrument is of great consideration in an
investigation. The detection efficiency which is the probability of detection when
the particle crosses it, varies widely. In most of the direct ionizing radiation, it is
nearly 1. After an event is detected, most of the instruments lose their sensitivity
for certain time called “Dead time”. In order that the counter efficiency be high, it
is important that the dead time be smaller than the mean time interval between
successive events. If r is the counting rate and td is the dead time then for high
efficiency, the condition rtd<<1, must be satisfied.
A perfect detector might have the following characteristics
i. 100 percent detection efficiency
ii. high-speed counting and timing ability
iii. good energy resolution
iv. linearity of response
v. application to virtually to all types of particles and radiations
vi. large dynamic range
vii. virtually no limit to the highest energy detectable
viii. reasonably large solid angles of acceptance
ix. discrimination between types of particles
x. directional information
xi. low background, and
xii. picturization of the event.
7.2
7.2Ionization
IonizationMethods
Methodsfor
forMeasurement
MeasurementofofRadiation
Radiation
Different types of detectors can be characterized by the nature of the interaction of
124
radiation with matter. Gas filled detectors operate by utilizing the ionization
produced by radiation as it passes through a gas. Such a counter consists of two
electrodes to which a certain electrical potential is applied. The space between the
electrodes is filled with a gas. Ionizing radiation, passing through the space
between the electrodes dissipates part or all of its energy by generating electron-
ion pairs. They are charge carriers that move under the influence of the electric
field. This induces a current on the electrodes, which may be measured or through
appropriate electronics, the charge produced by the radiation may be transformed
into a pulse, in which case particles are counted individually. A nucleonic pulse
originates as transient voltage change across the output end of a radiation detector,
as a result of charge deposited in the detector by the passage of ionizing radiation.
Radiation detector generating a charge pulse can be represented by a circuit
diagram shown in the Fig.
Figure 4: The electronic circuit of ionization chamber
Relationship between High Voltage and charge collected:
A radioactive source of constant intensity is placed at a fixed distance from a gas
counter. The high voltage (HV) applied to the counter may be varied with the help
of a potentiometer. An appropriate meter measures the charge collected per unit
time. If the HV applied to the counter is steadily increased, the charge collected per
unit time changes as shown in Fig.
125
Figure 2: Characteristics of a gas filled detector
Region I : When the voltage is very low, the electric field in the counter is not
strong, electrons and ions move with relatively slow speeds, and their
recombination rate is considerable. As V increases, the field becomes stronger, the
carriers move faster, and their recombination rate decreases up to the point where it
becomes zero. Then the entire charge created by the ionizing radiation is being
collected. That gives the saturation current known as Ionization region current.
Region II : The recombination rate is zero and no new charge is produced. This is
indicated as Ion saturation in Fig2.
Region III : The electric field is so strong, in a certain fraction of the counter
volume, that the electrons from the primary ionization acquire enough energy
between collisions to produce additional ionizations. The gas multiplication factor:
Ks i.e., the ratio of the total ionization produced divided by the primary ionization
is, for a given voltage, is independent of the primary ionization. The output of the
counter is proportional to the primary ionization. The pulse height of the output is
proportional to the energy dissipated inside the counter. Therefore, particle
identification and energy measurement are possible.
Region IV : Beyond the proportional region, the electric field inside the counter is
so strong that a single electron-ion pair generated in the chamber is enough to
126
initiate an avalanche of electron-ion pairs. This avalanche will produce a strong
signal with shape and height independent of the primary ionization and the type of
particle, a signal that depends only on the electronics of the counter. This region is
called the Geiger-Muller region.
Different types of gas filled counters take their name from the voltage region in
which they operate-
Region Name of the counter
I Ionization chamber
III Proportional counter
IV GM counter
7.3Ionization
7.3 IonizationChamber
Chamber
Operate in the ionization region. No charge multiplication takes place. Output
signal is proportional to the particle energy dissipated in the detector. Since the
signal is not large, only strongly ionizing particles such as alpha, protons, fission
fragments and other heavy ions are detected.
7.4
7.4Proportional
ProportionalCounters
Counters
Operate in region III. Charge multiplication takes place. Output signal is still
proportional to the energy deposited in the counters. Measurement of particle
energy is possible. Identification of the type of particle is possible.
7.5
7.5Geiger-Muller
Geiger-MullerCounter
Counter(GM
(GMCounter)
Counter)
Operate in region IV. It can be used for any kind of radiation. The signal is
independent of the particle energy and its type. It provide information only about
the number of particles. It has relatively long dead time (200 to 300 μs).
General Principles: A widely used radiation detector is a Geiger Muller detector
tube. Cross sectional view of a typical GM tube is shown in Fig.3. A GM tube
consists of a very fine central anode and a shell, which serves as the cathode. The
region surrounding the anode is filled with a gas, usually argon or neon, specially
selected for the ease with which it can be ionized. A high electrical field is
maintained between the electrodes.
127
Figure:3
The sensitive volume is the portion surrounding the anode responding to the
specific radiation. An energetic charged particle traversing through the sensitive
volume will have high probability of producing one or more ion pairs (electron and
positive ion). The electron is accelerated towards the anode and in a short distance,
gains sufficient kinetic energy to produce a second ion pair in a chance encounter
with a gas atom. These two electrons will now produce additional ion pairs and
thus an avalanche is developed in which an enormous number of electrons of the
order of 1010 are eventually collected by the anode. This charge which will be
collected in about 0.25s, appears across the capacitance of the tube plus the
associated circuitry to produce a voltage pulse of amplitude ranging from 0.25 to
10 volts with a duration of about 100s. These values depend upon the design of
the tube, its operating voltage and the characteristics of the external circuit. When
the voltage across the tube is such that it is operating in the GM region, all pulses
are of equal size irrespective of the number of ion pairs formed in the initial
ionizing event.
Operating Characteristic of a GM Tube :
When the tube is exposed to a constant radiation intensity and the voltage applied
on the tube is slowly increased, a voltage will be reached at which GM tube begins
to produce pulses as indicated by the recorder. This is the starting potential. As the
voltage is increased, very rapid increase in counting rate is observed. This voltage
is known as the threshold. Beyond the threshold further increase in the voltage
over certain range will produce little effect on the counting rate. This region is
known as the plateau. It should have a slope of less than 10% per 100 volts for
128
good tubes. Within the plateau region, the proper operating voltage is selected. The
operating voltage should be selected relatively close to the threshold voltage
(within the lower 25% of the plateau) to preserve the life of the tube. Also the
operating voltage should be selected at a point where the plateau shows minimum
slope. If the voltage is increased beyond the plateau region, the counting rate
begins to increase rapidly and the region of continuous discharge is reached. The
shape of the high voltage (HV) plateau is as shown in the Fig. and explained as
follows.
Figure 4
For very low voltage (V < Vs ) the counting rate is zero. The scaler does not
receive any signal because all the pulses are below the discriminator level. The
counting rate keeps increasing with high voltage (HV), since more and more pulses
are produced with a height above the discriminator level. This continues up to the
point when V = V1. For V > V1, all the pulses are now above the discriminator
level. Since all the pulses are counted, each pulse being recorded as one regardless
of its height, the counting rate does not change. This continues up to V = V2.
Beyond that point, the counting rate will start increasing again because the HV is
so high that spurious & double pulses may be generated. Counter should not be
operated beyond V = V2
Quenching of the discharge:
When the electrons are accelerated in the strong field surrounding the wire they
produce, in addition to a new avalanche of electrons, considerable excitation of the
atoms and molecules of the gas. These excited atoms and molecules produce
photons when they de-excite. The photons in turns, produce photoelectrons in other
129
parts of the counter. Thus the avalanche, which was originally located close to the
wire, spreads quickly in most of the counter volume. During all this time, the
electrons are continuously collected by the anode wire, while the much slower
moving positive ions are still in the counter and form a positive sheath around the
anode. When the electrons have been collected, this positive sheath, acting as an
electrostatic screen, reduces the field to such an extent that the discharge should
stop. However, this is not the case because the positive ions eject electrons when
they finally strike the cathode, and since by that time the field has been restored to
its original value, a new avalanche starts and the process just described is repeated.
Clearly some means are needed by which the discharges is permanently stopped or
quenched. Without quenching, a GM tube would undergo repetitive discharging.
There are two general methods of quenching the discharge.
External Quenching : In external quenching, the operating voltage of the counter
is decreased, after the start of the discharge until the ions reach the cathode, to a
value for which the gas multiplication factor is negligible. The decrease is achieved
by a properly chosen RC circuit. The resistance R (10 ohms or more) is so high
that the voltage drop across it due to the current generated by the discharge (id)
reduces the voltage of the counter below the threshold needed for the discharge to
start (Vo - id R). The time constant RC is much longer than the time needed for the
collection of the ions. As a result the counter is inoperative for an unacceptably
long period of time. In other words, its dead time is too long.
Internal quenching : The internal quenching method is accompanied by adding to
the main gas of the counter a small amount of a polyatomic organic gas or a
halogen gas. These have relatively large molecules, which tend to absorb the
fluorescent emissions of the noble-gas atoms. They also have smaller excitation
potentials than the latter, so their de- excitation photons have insufficient energy to
ionize the gas and propagate the discharge further. For satisfactory photon
quenching, the absorption spectrum of the quenching agent should match the
emission spectrum of the noble gas. Methane and ethanol both satisfy these
requirements.
GM counters using an organic gas as quenching agent have a finite lifetime
because of the dissociation of the organic molecules. Usually the GM counters last
for 108 to 109 counts. The lifetime of a GM detector increases considerably if a
130
halogen gas is used as the quenching agent. The halogen molecules also dissociate
during the quenching process but there is a certain degree of degeneration of the
molecules which greatly extends the useful lifetime of the counter.
Sensitivity of a GM tube :
GM tubes are not equally sensitive to , and radiations. Once the radiation
reaches the sensitive volume of the counter, the efficiency of detection is 100% for
, nearly 100% for and only 1 or 2% for radiation.
Dead Time and Recovery Time of GM Tubes :
It is found on close observation of oscilloscope that a small vertical pulse can
sometimes be seen closely following one of the normal height for a particular
applied voltage. These pulses occur when one ionizing event follows another at an
interval too short for the counter to have completely recovered, a situation due to
the fact that the positive ion sheath has not reached the cathode when the second
ionizing event occurs. The longer the interval between the ionizing events the
larger the second pulse will be, until it reaches its maximum. The time interval
between the first full pulse and the detectability of another full pulse depends on
the characteristics of the counter tube and is known as resolving time. This time
interval is made up of two parts. The first part is the dead time and is the time after
a count during which no pulse can be registered at all, even if an ionizing event
occurs, because the electric field has collapsed and has not yet been re-established.
The second part is the recovery time, a time of increasing sensitivity, during which
an ionizing event will give a pulse of amplitude less than that which is
characteristic of the particular tube at the applied voltage. During this time the
electric field is growing to its maximum value. At the end of the recovery time a
full pulse is recorded. This is illustrated in given Fig5 below.
Figure 5
131
Consider two radioactive sources of strength S1 and S2. Let n1, n2 be the respective
count rates recorded and n12 be the count rate recorded when sources are taken
together. Let be the resolving time. Let N1, N2 and N12 be the corrected count
rates respectively. Then we have
n1 n2 n12
N1 ; N2 ; N12
1 n1 1 n2 1 n12
we have
N1 + N2 = N12
substituting value of N1, N2 and N12 in above equation.
n1 n2 n12
1 n1 1 n2 1 n12
solving the above equation and neglecting the higher powers of we get
n1 n2 n12
2n1n2
7.6
7.6Self
SelfLearning
LearningExercise-I
Exercise-I
Q.1 Which type of particles towards GM counter is most sensitive?
Q.2 What is Giger region .
Q.3 What is dead time?
Q.4 Write down the principle of GM counter.
7.7
7.7Scintillation
ScintillationCounter
Counter
Construction: Scintillation counter consists of a photomultiplier tube to which is
fixed a scintillator. A high voltage (~kV) is applied between the photo-cathode and
the anode. The dynodes incorporated in the tube produce electron multiplication
and by the use of a voltage divider provide progressively larger voltage between
cathode and anode. Scintillators exist in several forms, crystals (organic or
inorganic), liquids, plastic solids and gases. The scintillation phenomenon depends
on the fact that suitable “flours” give off pulses of light when traversed by a
charged particle.
132
Figure 6: Block diagram of a scintillation counter.
This light is directed on to a photomultiplier cathode where it ejects electrons by
photo-electric effect. These electrons are multiplied in the dynode structure of the
tube. In each stage the number of secondary electrons is multiplied which are
finally collected at the anode and recorded as a pulse by suitable circuits. The
phosphor is in optical contact with the tube and is protected from external light. A
reflector surrounding the phosphor enhances light falling on the photo-cathode for
higher efficiency.
Mechanism: A charged particle passing through the phosphor loses energy by
ionization, excitation and dissociation of molecules close to its path, ultimately
light is emitted. The solid phosphor scan be basically divided into
i. organic
ii. inorganic crystals.
There are several important differences between the characteristics of organic and
inorganic scintillators, in regard to lifetimes, linearity of energy response,
temperature effects, fluorescence and conversion efficiency and vmax at which
maximum number of photons are emitted. The basic difference in the mechanism
for the light production is that light emitted by an inorganic crystal is primarily due
to the crystal structure, where as organic substances exhibit luminescence by virtue
of molecular properties.
133
Desirable Characteristics of Luminescent Materials:
i. The phosphor must have high efficiency for conversion of incident energy of
radiation or particles into that of the emitted luminescence. In the case of
inorganic phosphor material a small percentage impurity is essential while for
organic phosphors, material must be pure.
ii. The spectrum of the emitted light must closely match the spectral response of
the cathode of the photomultiplier used.
iii. The luminescent material must be transparent to their own luminescence
radiation.
iv. The material used must be a large optically homogeneous mass, either as a
single crystal without defects or in solution, solid or liquid, moulded or
machined to any convenient shape.
v. The phosphor must have a high stopping power for the radiation to be
detected.
vi. The rise and decay of luminescence during and after excitation should occur in
a short time.
vii. The phosphor must be stable against vacuum conditions and under prolonged
irradiation.
viii. The refractive index of the crystal should not be too high, otherwise light
will not be able to come out easily due to internal reflections.
Organic Scintillators:
Main mechanism is believed to be that of collisions which are responsible for
the energy transfer from the molecules, either by excitation transfer or by a
dipole resonance interaction.
The energy response, is not quite linear.
Light output is very much dependent upon the nature of the particle.
Lifetime is of the order of 10−9 to 10−8 sec.
The phenomenon of phosphorescence is absent.
The fluorescent conversion efficiency is generally smaller than the inorganic
phosphors, conversion efficiency.
134
Examples: anthracene, (max = 4400 A), diphenylacetyline, terphenyl naphthalene
and stilbene.
Organic phosphors are extensively used for fast neutron detection. The interactions
of fast neutrons with hydrogen produce fast recoil protons which can be detected
with high efficiency in large crystals.
Inorganic Scintillators:
In inorganic crystals, for example alkali halides notably NaI with thallium
impurity, charged particles may raise electrons into the conduction bands or into
excitation levels. The electron and the hole left move rapidly throughout the
crystal as an exciton until captured by the imperfection, giving up the energy in
the form of vibrational transfer or until captured by an impurity. The impurity
gets excited and acts as a scintillator. In the case of halides, thallium is added as
an impurity to the extent of 0.1 to 0.2 percent. These crystals are highly
transparent to their own radiation.
The light output from inorganic crystals like NaI is very nearly proportional to
energy loss down to about 1 MeV for protons and about 15 MeV for ’s.
The life time is of the order of 10−6 sec.
The phenomenon of phosphorescence which is delayed emission of photons can
in certain cases cause generation of secondary pulses which are indistinguishable
from the primary pulses. As sodium iodide is deliquescent, it must be protected
from moisture; nevertheless it is the most widely used inorganic phosphor. Large
size crystals up to several inches in diameter and length are available. It has a
high density and contains high Z atoms of Iodine and is an efficient detector for
gamma rays as the absorption cross section for the three important processes,
photoelectric, Compton and pair-production vary as Z4.5, Z and Z2 respectively.
Of the other inorganic phosphors, zinc sulphide is useful for alpha-particle
detection and lithium iodide for neutron detection, the relevant nuclear reaction
being
6Li+ n→3H +4He+4.8 MeV
Examples: NaI (thallium activated, max 4100 A), cesium iodide (cooled to
77 K), zinc sulphide (copper activated) and lithium iodide (europium activated).
135
Some of the inorganic phosphors have a high value of the refractive index (∼2).
Difficulty is experienced in getting light out of them.
Photo-Multiplier (PM) Characteristics:
The desired characteristics of Photo-multiplier (PM) are:
1. PM must have a photo cathode of large cathode area with an end-window.
2. PM must be of a high efficiency for converting photons into photo-electrons.
3. PM must provide a high gain.
4. It must provide a good signal-to-noise ratio. In the absence of light the output
from a photomultiplier consists of numerous pulses (noise) of various sizes,
principally due to thermal emission of electrons from the photo-cathode. This
constitutes the so-called dark current which depends on the photo-cathode
material. It can be reduced by cooling the cathode.
5. Examples: 56 AVP (Philips), 6810 A, 7264 (RCA), 6292 Du Mont. The
number of dyonodes varies from 10 to 15.
Light Collection:
A crystal scintillation counter is normally placed in a metal container. When
hygroscopic alkali halides are used, they are protected against moisture by sealing
the container. Good optical contact is made between the surface of phosphor and
the end face of PM with a layer of clear vacuum grease and by placing a good
reflector in optical contact with other crystal surfaces so that light which would
otherwise escape will be returned to the photomultiplier with improved efficiency.
A highly polished foil or a diffuse reflector such as magnesium oxide is used as a
specular reflector. When the arrangement is such that the PM can not be in direct
contact with the scintillator, lucite pipes can be used.
Electronic Equipment:
Figure:7
136
Figure7 is a block diagram of the electronic equipment attached to the PM. Pulses
from the anode of the PM which are small are passed through a pre-amplifier and
then to a linear amplifier and through a “window” of the differential analyzer, and
finally counted by the scalar. The high voltage can be varied to suite the given PM.
The gain of linear amplifier can be varied so that the input fed to the differential
analyzer is within the range of operation. The differential analyzer accepts pulses
of height between V and V+V , where V is the width of the window. The
pulse height is proportional to E.
Gamma Ray Spectroscopy with NaI (TL) Scintillator:
At low ray energy (< 100 keV) photoelectric absorption is the dominating
process. As ph ∝ Z4.5, most of the absorptions occur in Iodine, with the K-shell
electron (ionization energy Ek = 29 keV). The vacancy caused by the ejection of
electron is filled in by radiative transitions (mainly X-rays) from electrons
belonging to upper levels. If the resulting X-rays get absorbed then full energy (E)
is available and this corresponds to photo peak in the pulse height distribution.
However, in few events the X-rays escape. Hence energy equal to (E −Ek ) is
available. This results in the “Iodine escape peak”. The ratio of photons under
escape peak to those under photo-peak depends on E crystal size and experimental
geometry.
Figure:8
137
For E > 100 keV, Compton scattering also becomes significant. The “escape
peak” is not significant when the mean absorption length of the incident –rays
becomes greater than that of iodine X-rays. In the case of single Compton
scattering, the energy of escape radiation extends from E` to E, where
E` = E /(1 + 2) with = E/mc2 corresponds to the energy of the scattered
photon at 180◦ (back scattering). The corresponding energy deposited ranges from
(E –E`) to 0. There will be a broad Compton distribution with the Compton edge
occurring at energy (E – E`). There can also be external Compton scattering from
material outside such as the PM shielding. This gives rise to the “back scattering
peak”.
In the case of multiple Compton scattering the energy of escaping radiation
extends from 0 to E and the corresponding energy deposited is E to 0. For E >
2mc2 (threshold for pair production) two other peaks are observed, a single escape
peak at (E −mc2) and a double escape peak at (E −2mc2).
Below figures (9,10) show typical spectra obtained from rays incident on NaI
crystal from Cs-137 (661 keV) and Co-60 (1.17 MeV and 1.33 MeV), respectively.
The 661 keV photo peak, Compton shoulder, back scattering from material of the
phosphor and noise are indicated. The decay scheme is also shown.
Figure 9: (a) Pulse height spectrum of γ -rays from Cs-137 of energy 661 keV. (b)
Decay scheme for Cs137
138
Figure 10: (a) Pulse height spectrum of γ -rays of energy 1.17 MeV and 1.33 MeV.
The origin of γ -rays is shown in the decay scheme. (b) Decay scheme for 60Co
Energy Resolution:
The photo peaks shown in above Figs, are not sharp. It is important that the spread
in photo peaks be as small as possible, otherwise -rays of neighboring energies
cannot be resolved. Many factors contribute to the energy resolution of a
scintillation counter. These factors are:
i. Fluorescent radiation conversion efficiency (f )
ii. Efficiency for the collection of light by the cathode (b)
iii. Efficiency for the conversion of photo-electrons (c)
iv. Efficiency for collection of electrons which are accelerated to the first
dynode (p)
v. Total multiplication from all the dynodes (M)
If E is the particle energy and the average energy of the photons generated in the
crystal, then the number of photons emitted is Ef/. It follows that the number of
electrons finally collected at the output of the PM tube is equal to (Ef/)bcpM. For
various reasons there will be variation in the factors f, b, c,p andM. Of various
factors, however, the variation in c which arises due to the statistical fluctuations in
the number of photo-electrons released from the photo cathode is decisive for the
pulse height and is therefore the ultimate factor which limits the resolution. The
best resolution that is achieved is 6 % for 661 keV -rays from Cs-137 using NaI
139
phosphor and a 6292 Du Mont P.M. Note that E ∝E , so that the energy
resolution, E/E ∝ 1/E .
Applications and Advantages
1 Fast Timing-
For investigations which involve fast timing, the scintillation counters have a
decisive advantage over visual detectors. This aspect has been exploited in the
lifetime measurements of +, K+, capture times of − and in the discovery of p−
by time of flight method. In conjunction with Cerenkov counter or other
scintillation counters, it can be used as a “telescope” in coincidence or anti-
coincidence to avoid unwanted particles or events.
2 Scintillation Spectroscopy
Spectrometry of heavy charged particles by scintillation technique is usually done
with the use of inorganic crystals. However, a number of organic compounds are
also found useful. Organic scintillators like anthracene have a linear response for
electrons, but for heavier particles the pulse-height energy relationship exhibit
nonlinearity. For this reason, organic scintillators are preferred to inorganic
crystals for electron spectroscopy as their effective low atomic number causes
substantial improvement for backscattering compared with inorganic crystals,
except for very low energy electrons.
3 Gas Scintillation Counters
Gas scintillation counters have the merit of short decay times (∼10−9 s), large light
output per MeV independent of ionization density, and their availability in a wide
range of Z and density. Fission fragments in the presence of heavy background of
’s can be discriminated. Also, because of low stopping power and small pulse
height for -rays of nuclear origin, relativistic charged particles can be separated
from an intense radiation background
7.8
7.8Self
SelfLearning
LearningExercise-II
Exercise-II
Q.1 Differentiate between the characteristics of organic and inorganic
scintillators.
Q.2 What are the desirable Characteristics of Luminescent Materials.
140
Q.3 Write down the characteristics of Photo-Multiplier (PM).
7.9
7.9Answers
AnswerstotoSelf
SelfLearning
LearningExercises
Exercises
Answers to Self Learning Exercise-I
Ans.1: Charge particles
Ans.2: Beyond the proportional region, the electric field inside the counter is so
strong that a single electron-ion pair generated in the chamber is enough to
initiate an avalanche of electron-ion pairs.
Ans.3: After an event is detected, most of the instruments lose their sensitivity for
certain time called “Dead time”.
Ans.4: See Section 7.5
Answers to Self Learning Exercise-II
Ans.1: organic and inorganic scintillators are different not only in regard to
lifetimes, linearity of energy response, temperature effects, fluorescence and
conversion efficiency and vmax at which maximum number of photons are
emitted but also in the mechanism for the light production. light emitted by
an inorganic crystal is primarily due to the crystal structure, where as
organic substances exhibit luminescence by virtue of molecular properties.
Ans.2: See Section 7.7
Ans.3: See Section 7.7
7.10Exercise
7.10 Exercise
Q.1 Compare and contrast ionization chambers, proportional counters, and
Geiger-Muller tubes.
Q.2 Describe the construction and explain the operation of a photomultiplier
tube.
7.11
7.11Summary
Summary
In this chapter we discuss various types of detectors. Firstly we introduce
Ionization chamber followed by Proportional counter, Geiger-Muller counter and
Scintillation counter.
141
7.12
7.12Glossary
Glossary
Background radiation :The radiation of man's natural environment originating
primarily from the naturally radioactive elements of the earth and from the cosmic
rays. The term may also mean radiation extraneous to an experiment.
Geiger counter : A Geiger-Müller detector and measuring instrument. It contains
a gas-filled tube which discharges electrically when ionizing radiation passes
through it and a device that records the events.
Ionizing radiation : Radiation that is capable of producing ions either directly or
indirectly.
Scaler : An electronic instrument for counting radiation induced pulses from
radiation detectors such as a Geiger-Muller tube.
Scintillation counter : An instrument that detects and measures gamma radiation
by counting the light flashes (scintillations) induced by the radiation.
References
Referencesand
andSuggested
SuggestedReadings
Readings
1. Particle Physics by A. Kamal 2014.
2. Engineering Physics, by Raghuvanshi, G. S. Raghuvanshi.
3. Nuclear and particle physics by B. R. Martin 2006.
4. Nuclear Energy by Raymond L. Murray, 2000.
5. R.R. Roy and B.P. Nigam: Nuclear Physics (Willey -Easter, 1979).
142
UNIT-8
Detectors-II
Structure of the Unit
8.0 Objectives
8.1 Solid state detectors (Diffused junction detector, Surface barrier detectors)
8.2 Nuclear Track Detectors
8.3 Nuclear Electronics and Data Collection
8.4 Nuclear Statistics
8.5 Self learning exercise I
8.6 Multi-Wire Proportional and Drift Chambers
8.7 Nuclear emulsions
8.8 Self learning exercise II
8.9 Summary
8.10 Glossary
8.11 Answers to self learning exercises
8.12 Exercise
References and Suggested readings
8.0
8.0Objectives
Objectives
After interacting with the material presented here students will be able to
understand the working of
Diffused junction detector
Surface barrier detectors and
Nuclear detectors
Multiwire proportion chambers
In this chapter we will also discuss nuclear emulsion and the techniques and
analysis of tracks.
143
8.1
8.1Solid
SolidState Detectors
State (Diffused
Detectors Junction
(Diffused Detector,
Junction Surface
Detector,
BarrierSurface
Detectors)
Barrier Detectors)
The several types of semiconductor detectors that exist today differ from one
another because of the material used for their construction or the method by which
that material is treated. The rest of this section describes briefly the method of
construction and the characteristics of the most successful detectors -made of
silicon or germanium-and two promising ones made of CdTe and HgI2.
1. Surface Barrier Detectors:
Silicon of high purity, usually n-type, is cut, ground, polished, and etched until a
thin wafer with a high-grade surface is obtained. The silicon is then left exposed to
air or to another oxidizing agent for several days. As a result of surface
oxidization, surface energy states are produced that induces a high density of holes
and form, essentially, a p-type layer on the surface (Figure). A very thin layer of
gold evaporated on the surface serves as the electrical contact that will lead the
signal to the preamplifier. In Fig., X,, is the depth of the sensitive region, t is the
total silicon thickness, and D is the diameter of the detector. The size of the
detector is the length (or depth) Xo.
2. Diffused-Junction Detectors:
Silicon of high purity, normally p-type, is the basic material for this detector type.
As with surface-barrier detectors, the silicon piece has the shape of a thin wafer. A
thin layer of n-type silicon is formed on the front face of the wafer by applying a
phosphorus compound to the surface and then heating the assembly to
144
temperatures as high as 800-1000" C for less than an hour. The phosphorus
diffuses into the silicon and "dopes" it with donors (Figure). The n-type silicon in
front and the p-type behind it form the p-n junction.
Both surface-barrier and diffused-junction detectors are used for the detection of
charged particles. To be able to measure the energy of the incident radiation, the
size Xo of the detector should be at least equal to the range of the incident particle
in silicon. The value of X0, depends on the resistivity of the material (which in turn,
depends on impurity concentration) and on the applied voltage.
8.2
8.2Nuclear
NuclearTrack
TrackDetectors
Detectors
The passage of highly ionizing radiation through an insulating solid leaves a wake
of destruction in the material. In covalently bonded materials, the chemical
structure of the material along the track can be significantly and permanently
changed by the passage of a single energetic ion. Certain polymeric (plastic)
materials and the mineral mica (a form of silicon dioxide) are particularly sensitive
to such radiation damage. The original radiation damage remains localized on the
molecular scale but is not visible without enhancement. However, the track can be
expanded by chemical etching from the molecular scale (nanometers) up to the
microscopic scale (μm).
145
Advantages: Nuclear track detectors are very simple and very efficient detectors
of rare events that produce highly ionizing radiation. Carefully prepared and
scanned track detectors have been used to identify individual rare decays. The
detectors are integrating in that the damage caused by a track is not spontaneously
repaired.
Drawback: The drawback to track detectors is that the tracks are small and can
only be observed with a microscope. In the past, scanning by eye was extremely
labor intensive and prone to error. Modern computer--‐controlled scanning has
improved the speed and reliability of the analysis.
Plastic track detectors that are sensitive to alpha particles are used extensively in
commercial radon detectors. Chemical etching of the material takes place on all
surfaces that are exposed to the etching solution. The exposed surfaces of the
material are eroded along with the material along the track. Therefore, the rate of
etching has to be carefully controlled to get the maximum amount of information
from the track.
Notice that etching of a uniform track will generally form a circular cone because
the material will be more easily removed from the surface than from deep along
the track. Mica tracks are diamond-shaped due to the lattice structure as opposed to
being circular.
Nuclear emulsions are closely related "track detectors" that trace their origins to
the original discovery of radiation by Becquerel. Nuclear emulsions are very fine-
grained photographic film. The film is "exposed" by the passage of radiation
through it and the grains of AgC1 are activated by the ionization. The film is
developed and with careful handling and microscopic observation, the track or path
of individual particles can be traced. Occasionally, a particle interacts with a
nucleus in the emulsion, creating many fragments or particles, and the tracks of the
reaction products can be traced. The emulsion is also sensitive to the rate of
ionization and the nature of the particle in each track can often be determined. On
the other hand, most people are familiar with the shadow images of skeletal
features taken with x-rays. The x-rays are absorbed and scattered more efficiently
by the heavy elements in bones (essentially calcium) than by the light elements in
soft tissue (carbon, oxygen, hydrogen) and create a shadow. The grains in the
146
emulsion are then exposed by the transmitted x‐rays and are developed to form the
negative image.
8.3
8.3Nuclear
NuclearElectronics
Electronicsand
andData
DataCollection
Collection
All of the nuclear radiation detectors produce electronic pulses in response to the
interaction of some ionizing radiation. These signals are processed by standardized
nuclear instrumentation modules (NIM) electronics to count the number of pulses
or to more fully analyze the size or even the shape of the signal. In addition,
computer‐based electronics in the CAMAC (Computer Automated Measurement
and Control) system are used to measure the time relationships of pulses, the pulse
heights, and the signal shapes. The signals are recorded and stored by computers
for later analysis. An important feature of scientific studies with radio activities
and with nuclear beams is that the data must be collected as rapidly as possible
usually during a very limited time. A radioactive source will decay away after
being produced and cannot be "stopped" because the scientist is not ready to use it.
Similarly, the nuclear reactions induced by particle beams take place in a very
short time and must be recorded when they occur. Then after a set of events has
been collected “on-line,” the data are analyzed “off‐line.”
We will give a very brief overview of the kinds of modules used. CAMAC and
NIM electronics fall into three broad categories,
linear electronics that maintain a linear relationship to the size of the initial
signal,
logic circuits that provide only a standard (or single sized) pulse indicating
that a given logical condition was met, and
data-acquisition modules to measure the signals and record the data.
One should realize that with modern high density electronics the functions that we
will describe can correspond to a single electronic module or may be condensed
into a single integrated circuit. Therefore, we will only describe the functions
performed by the electronic modules and not specific equipment. The output of
most detectors is an electrical pulse that carries information about the energy
deposited in the detector, the time of the interaction, etc. Linear electronics are
described as modules that preserve and extract information about the energy
147
deposit in the detector from the detector signal.
A typical pulse‐height analysis system is shown in figure. The signal from the
detector is given a preliminary amplification and shaping by a preamp before being
sent through a coaxial cable to a linear amplifier. This is done to prevent noise in
the cable from destroying the tiny detector signal. In the amplifier the signal is
further amplified and shaped before analysis. The height of the pulse is related to
the energy deposited in the detector. The analog-to-digital converter (ADC)
converts the signal from the amplifier into digital data (a number of standard
pulses) thus measuring its size. The ADC could be contained on a plug-in card in a
personal computer (used to measure the distribution of pulses from a single
detector monitoring a radioactive source) or it might be one of many identical
ADC units in a CAMAC module (used to record the signals from many detectors
monitoring nuclear collisions simultaneously) .Logic modules are used to monitor
the counting rate of single detectors and the relative times at which radiation is
detected. A fast signal derived from the detector itself, the preamplifier, or from a
timing-filter amplifier is sent to a discriminator. The discriminator produces an
output pulse with a fixed shape (generally square) and size when the input signal
crosses a reference. Discriminators usually have multiple identical output signals.
The logic pulses can be sent to a scalar that simply counts the number of pulses, to
a count rate meter to monitor radiation rates or doses, and to a time-to- amplitude
converter (TAC) to measure the relative times of arrival of two or more logic
signals.
148
8.4
8.4Nuclear
NuclearStatistics
Statistics
Radioactive decay is a random process. The number of nuclei in a sample of
radioactive material that decay in any time period is not a fixed number but will
differ, usually, for various time periods. This point can be readily shown by
making repeated measurements of the activity of a long-lived radionuclide, each
for the same time duration. The results of such an experiment might be shown in as
a distribution function, by “binning” the data (Figure: Typical Sequence of Counts
of a long-Lived Sample (170Tm)*).
We can now ask ourselves if we can understand this distribution function.
Statisticians have given us mathematical models that describe these and other
similar distribution functions. As a background for our discussion of how to extract
the maximum amount of information from these data, let us consider some of these
models. The most general model to describe radioactive decay is the binomial
distribution. For a process that has two outcomes (success or failure, decay or no
decay), we can write for the distribution function P(x)
n!
P( x ) p x (1 p) n x
( n x )! x !
where n is the number of trials where each trial has a probability of success p and
149
P(x) is the predicted probability of getting x successes. Applying this distribution
to radioactivity, P(x) might be taken as the probability of getting x counts in a
given time interval and p=λ∆t where ∆t is a time short compared with the
measurement time and the half-life. Note that x and n are both integers. Typical
binomial distribution functions are shown in Figure.
The binomial distribution function is cumbersome and a simplification can be
made. If the probability of success p is small (p<<1) (the measurement time is very
short compared with the half-life), we can approximate the binomial distribution
by the Poisson distribution. The Poisson distribution is written as
xm x
P( x ) exp( xm )
x!
where xm= pn
Thus we have a simplified distribution characterized by one parameter, xm
compared to two parameters in the binomial distribution. The Poisson distribution
is an asymmetric distribution as shown in Figure.
Besides being a more tractable function to use, the Poisson distribution has certain
important properties that we will use in analyzing radioactivity data.
150
Let us consider a parameter, the variance, σ2, which expresses something about
the width of the distribution of values about the mean, xm.
For a set of N measurements, we can calculate
N
(x i xm ) 2
2 i 1
N 1
For a binomial distribution
2 np (1 p )
Which is cumbersome to use but, for a Poisson distribution, we can show that
2 xm
( xm )1/2
This illustrates the important point that these distribution functions are models, not
physical laws, and when they are applied to finite data sets, their predictions may
deviate from observation. The Poisson distribution can be applied also to describe
the action of detectors. For example, suppose the interaction of a γ-ray photon
with an inefficient scintillator produced, on average, 3.3 photoelectrons from the
photocathode. The probability of producing no photoelectrons (not seeing the
event) is given by the Poisson distribution as
P(0)= exp(-3.3) = 3.7%
Thus 3.7% of the events will be missed due to “statistical fluctuations”. A further
simplification of the parent binomial distribution occurs when the number of
successes is relatively large, i.e., we get more than about 30 counts in a
measurement. Then the binomial distribution can be represented as a normal or
Gaussian distribution. Here we write
151
1 ( x xm ) 2
P( x ) exp( )
2 xm 2 xm
This analytical approximation is symmetric. As shown in Figure, 68.3% of the
measured values lie within ±1σ of the mean, xm.
Furthermore 95.5% of all measurements lie within ±2σ of the mean and 99.7% lie
within ±3σ of the mean. The full width at half maximum (FWHM) is 2.35σ .
Thus for a single measurement of a count rate of 100, we would estimate that σ =
10. We could say, with a 68.3% chance of being correct that the true rate was
between 100-10=90 and 100+10=110. With 95.5% certainty, we could say the true
rate lies between 80 and 120. Generalizing, we can quote the results of a
measurement as x'+ nσ where n is related to the probability that an infinite number
of measurements would give a value within the quoted range. For n =
0.6745,1,1.6449,1.96,2,2.5758,3, the “confidence limits” are 50%, 68.3%,
90%,95%,95.5%, 99%, and 99.7%, respectively. Commonly people will quote the
results of a measurement as x ± σ. One should remember that doing so means one
will be wrong 31.7% of the time, i.e., the mean count rate will be outside x ± σ. If
this risk is not acceptable, one should pick a greater confidence level, i.e., 2 σ, 3
152
σ, etc. Another distribution function of interest relates to the distribution of time
intervals between successive counts. We know the average time between counts is
(1/count rate). The distribution of time intervals is given by the interval
distribution. This distribution (applicable to all random events) states that for a
process with an average time between events tm, the probability of getting a time t
between successive events is
1
I (t ) exp( t / tm )dt
tm
For radioactive decay tm= 1/ λ
This distribution function is shown in Figure.
Note the most probable time between events is zero. Random events (counts,
natural disasters, etc.) occur in “bunches.” Let us summarize how we describe the
statistical uncertainty in measurements of radioactivity. If we measure the activity
of a sample (+background) as 64 counts in 1 minute, then we estimate
(S+B)=64cpm
with an uncertainty σ S+B
σ S+B= 8 cpm
What if a second measurement with no sample showed a background of 10 counts
in 1 minute? We would then estimate
153
B = 10 cpm
σ B= (10)1/2= 3.2 cpm
If we consider two independently determined numbers and their uncertainties
(standard deviations), A±σa , B±σb, we can write down, some rules for the
uncertainty in the result of some common mathematical operations. We would
calculate that for our sample and background counting case,
Net rate = (sample + background) ‐ (background)
=64 -10= 54cpm
Uncertainty in net rate = (82 + 3.22)1/2 = 8.6 cpm
Up to now we have carefully restricted our discussion of nuclear statistics to cases
where l-min counts were taken. If the number of counts recorded in 1 min was x,
then the counting rate has been quoted as x ± (x)1/2 cpm. Suppose, however, that
we recorded 160 counts in 5 min. What would be the standard deviation of the
average counting rate (in cpm)? The best estimate of the mean number of counts in
the 5-min period would by 160 ± (160)1/2 that is, 160 ± 13 counts. The average rate
would be 160/5 ± 13/5 = 32 ± 3 cpm. In general, therefore, the rate R is given as
R=(number of counts recorded)/(measurement time)=x/t
The standard deviation of the rate, σ R, is
σ R = (x)1/2/t=(R*t)1/2/t = (R/t)1/2
Thus for the preceding example we could have calculated directly that
σ R = (R/t)1/2=(32/5)1/2=3
Often we wish to compute the average of two numbers, x1, and x2, both of which
have an uncertainty denoted by their standard deviations σ 1 and σ 2, respectively.
The best average of these two numbers is not the simple average but weighted
average xm, given by
x x 1 1
xm 12 22 / 2 2
1 2 1 2
x1 wx2
xm
1 w
154
2
where w 1
2
In short, each number is weighted by the inverse of its standard deviation squared.
For the weighted average of N values, xi, with standard deviation, σ i, we have
N
x N 1
xm i2 / 2
i 1 i i 1 i
The uncertainty or standard deviation of x is given by
1/2
N 1
xm 1 / 2
i 1 i
For example, suppose that we make two independent measurements of an activity,
obtaining results of 35 ± 10cpm and 46 ± 2cpm. The weighted average of the two
measurements is
w= (10/2)2=25
xm = (35+25.46)(1+25)≅ 46 cpm
The standard deviation of the weighted average is
σ x= ((100+(25)2(4))/(262))1/2
1
x 1/ 2
2
1 1
100 4
Thus we would say that the average rate was 46 ± 2 cpm.
Rejection of Abnormal Data
In our discussions so far, we have only considered the uncertainty in the
experimental data due to the randomness of radioactive decay. But there may also
be systematic error that contributes to the overall uncertainty in the data. As a
result, when we make repeated measurements of a sample activity under seemingly
identical situations, we will find occasionally one measurement that differs from
the others by a large amount. If included in the average, this abnormal observation
may cause significant error. When are we justified in rejecting such data? One
criterion for rejecting such data is to reject suspected values that deviate from the
155
mean by more than 2σ or 3σ. The probabilities of ccurrence of such deviations are
4.5 and 0.27%, respectively. What about the question of whether a detector or
counting system is working properly? For example, the data in do not exactly
match a Poisson or normal distribution. Was the counting system malfunctioning?
One parameter that we can calculate that will help us answer such questions is 2
(chi‐squared). Formally
N
( x i xm ) 2
2 i 1
xm
Setting Upper Limits When No Counts Are Observed
Suppose our experiment failed to detect a type of decay we were seeking: What
can we say about its occurrence? The simplest answer is what is termed the “one-
event upper limit”. We assume that you had detected one event, and calculate the
resulting decay rate, cross section, etc., taking into account detection efficiencies,
solid angles, etc. A more sophisticated answer can be obtained by using the
properties of a Poisson distribution. The probability of observing n events if the
mean value is μ is given as
n
(n / ) e
n!
The probability of observing 0 events in a time period T for a process with mean
rate λ is
(0 / t ) e t
It can be shown that the upper limit on the rate (when zero counts are observed),
λ 0 , is given by
1
0 ln(1 CL )
T
Where CL is the confidence limit you wish to attach to your upper limit. (If you
want to quote an upper limit with 95% confidence, then CL = 0.95.)
8.5Self
8.5 SelfLearning
LearningExercise-I
Exercise-I
Q.1 Write down the formula for binomial distribution.
Q.2 Write down the drawback of Nuclear Track Detectors.
156
Q.3 Sketch figure of Diffused junction detector.
Q.4 Explain the nuclear detector electronics.
8.6
8.6Multi-Wire
Multi-WireProportional
Proportionaland
andDrift
DriftChambers
Chambers
The proportional chamber advances by virtue of the fact the voltage pulse it
measures is able to provide information on the particle’s energy as well.
The multi-wire proportional chamber or MWPC advances this further - instead of
having one anode wire surrounded by a cathode wall or plate, multiple ‘sense
wires’ are equidistantly spaced symmetrically between two parallel plates. Wire
spacings are typically a few millimetres. A nearly uniform electric-field develops
between the cathode plates, distorted only near the sense wires. Each wire acts as a
separate counter - when a charged particle passes through the chamber leaving a
trail of electron-ion pairs, the electrons drift to the nearest wire and cause a voltage
pulse. By placing another such configuration at 900 to the first, thus forming a grid,
and marking off the wires that produce a pulse, the path of the charged particle is
revealed.
Applying a magnetic field perpendicular to the direction the particle is travelling
in, will cause it to spiral due to the Lorentz force. This will reveal how the particle
157
is charged and what its momentum is.
A typical gas composition for multi-wire proportional chambers is the ‘magic gas’
mixture comprising 75% argon + 24.5% isobutane + 0.5% freon.
Drift chambers:
The resolution of multi-wire proportional chambers can be dramatically enhanced
by taking into consideration the time the electrons take to drift from the point
where they were liberated to the sense wire, where they are detected. Thus one can
infer the distance at which the charged particle passed the wire. This improves the
spatial resolution and allows for wider wire spacing on the order of centimeters.
Wider wire spacing distort the uniform field less, but increase the drift time, hence
these ‘drift chambers’ are not ideal for use in colliders with high collision rates, or
in triggers. In order to calculate the distance an electron has travelled it is
necessary to understand its velocity in the electric-field. The uniformity of the field
must be more carefully controlled than it is in a multiwire proportional chamber: to
this end, the anode sense wires are alternated with cathode field wires that ‘correct’
the field distortion caused by the sense wires, restoring uniformity throughout the
chamber. Drift velocities under electric-fields
158
8.7
8.7Nuclear
NuclearEmulsions
Emulsions
Composition:
Photographic Emulsions or Nuclear Emulsions differ from ordinary optical
emulsions by a higher silver-bromide content, smaller average crystal diameter and
much greater thickness. The silver-halide (mainly silver bromide with 5 % silver-
iodide) crystals are embedded in gelatin (HCNO). The gelatin is usually made from
clippings of calf hide, ear and cheek or from pig skin and bone. The main function
of gelatin is to keep the silver halide crystals well dispersed in the medium and to
prevent clamping of the crystals. Atomwise, the AgBr group and HCNO groups
compromise 25%and 75 % respectively. But the interactions with medium and
high energy particles take place with a frequency of 70 % in AgBr, 20 % in CNO
and 5 % in H. The emulsion sheets called pellicles of standard size 400μm or
600μm are stacked with one on the top of the other before the exposure in order to
increase the volume. A variety of emulsions of different crystal sizes have been
manufactured which differ in sensitivity. The type G5, L5 (Ilford), NTB (Kodak),
ET-7A (Fuji) and Nikfi-R with crystal size in the range 0.2μm–0.28μm are highly
sensitised and are capable of recording relativistic particles (β∼1). K2 and L2 are
less sensitised and record protons up to β=0.4. K1 is less sensitised and record less
protons up to β=0.12. K0 is least sensitised and is used mainly for fission studies.
Latent Image:
When a charged particle moves through emulsion energy is absorbed by the silver
halide crystal, and under the action of reducing agent is converted into metallic
silver. The physical condition which renders the crystal developable is called
“latent image”. The latent image will fade if too much time elapses between
irradiation and development, similar to ordinary photography.
Processing:
Stripped emulsions are first mounted on glass before processing. For uniform
development, it is essential that the developer, for example amidol, permeates the
thickness of emulsion. For this reason, the plates are bathed in the developer at low
temperature (0–5°C) so that the developer is permitted to penetrate but the
development will not ensue. Now, if the temperature is raised to say 23°C, the
159
development ensues. This is called high temperature development. After the
development stage, the plates are “fixed”, washed and dried in alcohol.
Techniques:
Events are analyzed with the aid of special type of microscopes with smooth
movable stages and high power oil objectives and eyepieces with graticules
capable of giving magnifications as high as 2700. After processing, normal
emulsion shrinks by a factor of 2–2.5. The shrinkage factor is taken into account in
the dip measurements of angles. For particles, which stop within the emulsion
stack, Range-Energy Relation of the type (1-101) is used.
Ionization measurements are made either by counting grains or blobs for
relativistic particles or by counting blobs and gaps of length > l, for non-relativistic
particles, and determining the exponent g from the relation
H = Be−gl
where H and B are gap and blob density, respectively. Blobs are unresolved grains
and gap is the space separating two successive grains or blobs, as shown in Fig.
For energetic particles, the parameter p (momentum times velocity) can be found
out from multiple scattering measurements by essentially measuring the y-
coordinates of the track along the axis, at constant intervals called “cell’s”. The
arithmetic average of second differences is given by,
| D2 | | y1 2 yi 1 yi 2 |
and p is given by the relation
3
Kt 18.1
2
p
D2
where K = 28 is the scattering constant, for β >1, D2 is in μm, t = cell length in
160
mm and p in GeV/c. The quantity t 3/2 arises due to the fact that the scattering angle
θ = D/t . The factor 18.1 arises due to conversion of degrees into radians. The
choice of cell-length is such that the signal-to-noise ratio is greater than 2–3.
Multiple scattering technique with constant cell method works provided the energy
loss over the tracks is not significant. In order that the method be useful, it is
important that the spurious scattering and distortion resulting from the processing
of mulsions be small and that the stage noise, which arises due to the non-linear
motion of the stage be negligible.
Charge of the particle can be determined from δ-ray counting (AAK, 1, 1) or from
photometric measurements; for example, the fluxes of heavy primaries of Cosmic
rays have been determined from emulsion exposures in balloons or rockets
following this procedure.
Particles are identified from their mass determinations. In this context we recall
from (AAK, 1, 1),
i. Range measurement gives energy of the particle
ii. Ionization measurement gives the velocity
iii. Multiple Scattering measurements give p .
iv. δ-ray density measurement gives z of the particle.
161
For singly charged particles, combination of any two parameters arising in (i), (ii)
and (iii) uniquely fixes the mass of the particle since velocity must be eliminated.
Thus, the plot of ionization (I ) versus residual range (R) gives a family of curves
for particles of different mass, Fig. Notice that for the given I, the ranges are in the
ratio of the masses. The method is very extensively used for particles which are
brought to rest. Masses can be estimated with an accuracy of about 10% from a
single measurement.
The method can be extended for identifying particles which are not arrested in the
emulsion stack, if an appreciable change in ionization over a known distance is
determined.
At higher energies, combination of (ii) and (iii) in favorable cases permits the
identification of particles. (Fig) At still higher energies, the curves cross each
other and the identification becomes difficult or even impossible. On the other
hand, energy measurements can seldom be made from multiple scattering method
with an accuracy better than 10–15 % due to the presence of spurious scattering. At
energies greater than few GeV, the measurements are rendered meaningless if the
noise due to spurious scattering competes with the Coulomb’s signal. Sometimes
in favorable cases it has been possible to extend the energy measurements up to
15–20 GeV in cosmic ray jets by making relative scattering measurements—a
method in which multiple scattering measurements are made with reference to a
neighboring track due to an ultra relativistic particle so that spurious scattering and
162
stage noise which affect both the tracks similarly are eliminated.
Advantages:
1. High Stopping Power and High Spatial Resolution
2. High Angular Resolution The angular resolution is unsurpassed. This aspect
has been exploited in the determination of the magnetic moment of Λ0.
3. Compactness In situations where compactness of equipment is essential,
emulsions can be conveniently used. For example, they can be sent in balloons or
rockets to high altitudes and recovered conveniently after the required exposure.
Further, they are economical.
4. Radiation Length Because of high stopping power and short radiation length
huge electromagnetic cascades can be contained in a large stack and the complete
development and final degradation can be studied in detail.
5. Loading It is possible to load emulsions with H2O, D2O, Li2SO4, Th(NO3)4, UO2
etc. to study reactions with elements which are not contained in normal emulsions.
Limitations:
1. Composition Invariability
The composition of nuclear emulsions can not be changed arbitrarily so that
interaction studies are limited only to those nuclei which are present in normal
emulsions, although loaded emulsions in limited concentration have been used
with some difficulty.
2. Minuteness of Volume Because of minuteness of volume of emulsion under
study in the microscope it is exceedingly difficult to find correlated events even 1
cm or so apart.
3. Continuous Sensitivity Because of continuous sensitivity the background tracks
are a source of nuisance. The best available emulsions from the stand point of
sensitivity lack discrimination and all highly ionizing particle tracks are saturated.
4. Distortion and Spurious Scattering
Emulsion which has a gelatin base is subject to distortion in the processing regime.
This can seriously affect the range and angle measurements. Spurious scattering
can interfere with Coulomb’s signal in multiple scattering measurements.
5. Scanning It usually takes several months involving a large group of Physicists
163
and scanners to scan and analyze events of statistical significance.
6. The Study of Elementary Interactions
Since only 5 % of the interactions take place with hydrogen and 95 % in complex
nuclei of emulsion, the interactions in the latter are obscured by secondary effects.
Although hydrogen density in emulsions is comparable with that in hydrogen
bubble chamber, the latter is by far better suited in so far as the elementary
interaction studies are concerned.
Discoveries Made with Photographic Emulsions
Major discoveries of fundamental importance included the particles π+, π−, π0, K+,
K − mesons, several decay modes of K+ mesons (two-body and three-body decay
modes), the hyperons, hyper fragment, double-hyper fragment, the composition of
primary cosmic rays etc. Reliable mass measurements of various types of mesons
and the ∑ +and Λ0 hyperons, and their mean life times were first carried out in
emulsions.
8.8
8.8Self
SelfLearning
LearningExercise-
Exercise-IIII
Q.1 Define latent image?
Q.2 What is the gas composition used in multi-wire proportional chambers?
Q.3 Write down the advantage and limitation of nuclear emulsion.
Q.4 Discuss workings of Multi-Wire Proportional and Drift Chambers.
8.9
8.9Summary
Summary
In this chapter we discussed various types of detector and nuclear detector
techniques.
8.10
8.10Glossary
Glossary
Background radiation: The radiation of man's natural environment originating
primarily from the naturally radioactive elements of the earth and from the cosmic
rays. The term may also mean radiation extraneous to an experiment.
Ionizing Radiation : Radiation capable of producing ions or charged particles.
Ionizing radiation includes alpha, beta, gamma, and X-rays.
Multiwire Proportional Counter : Particle detector using changes in the current
164
in wires due to the passage of ionizing particles nearby.
8.11
8.11Answer
AnswertotoSelf
SelfLearning
LearningExercises
Exercises
Answers to Self Learning Exercise-I
n!
Ans.1: P( x) p x (1 p) n x
( n x)! x !
Ans.2: See section 8.2
Ans.3: See section 8.1
Ans.4: See section 8.3
Answers to Self Learning Exercise-II
Ans.1: The physical condition which renders the crystal developable is called
“latent image”.
Ans.2: Mixture comprising 75% argon + 24.5% isobutane + 0.5% freon.
Ans.3: Section 8.7
Ans.4: Section 8.6
8.12Exercise
8.12 Exercise
Q.1 Write a short note on
(i) Diffused junction detector, (ii)Surface barrier detectors
(iii) Multiwire proportional chamber (iv)Nuclear emulsions
Q.2 Explain Different type of distribution function use to analyze nuclear data.
References
Referencesand
andSuggetsed
SuggetsedReadings
Readings
1. Measurement and Detection of Radiation by Nicholas Tsoulfanidis, 2013.
2. Modern Nuclear Chemistry by Walter D. Loveland, David J. Morrissey, Glenn
T. Seaborg, 2005.
3. Particle Physics by Anwar Kamal, 2014
4. Engineering Physics, by Raghuvanshi, G. S. Raghuvanshi.
5. Nuclear and particle physics by B. R. Martin 2006
6. Nuclear Energy by Raymond L. Murray, 2000.
7. R.R. Roy and B.P. Nigam: Nuclear Physics, 1979.
165
UNIT-9
Complex Nuclei : Shell Theory
Structure of the Unit
9.0 Objectives
9.1 Introduction
9.2 Magic number
9.3 The Shell theory potential
9.4 Allowed orbits in the Shell theory Potential
9.5 Self learning exercise I
9.6 Filling of the orbits in the Shell theory Potential
9.7 Magnetic Dipole Moments
9.8 Shell model failures
9.9 Self learning exercise II
9.10 Summary
9.11 Glossary
9.12 Answers to self learning exercises
9.13 Exercise
References and Suggested Readings
9.0Objectives
9.0 Objectives
After interacting with the material presented here students will be able to
understand the nuclear shell structure. They can also be able to calculate parity,
spin and magnetic moment of a given nucleus.
9.1
9.1Introduction
Introduction
There are two basic types of simple nuclear model-
1. Collective body with no individual particle states. An example is the Liquid
Drop Model which is the basis of the semi-empirical mass formula.
166
2. Individual particle model with nucleons in discrete energy states for example
the Fermi Gas Model or the Shell Model.
In this chapter we will discuss details of nuclear shell model.
9.2
9.2Magic
MagicNumbers
Numbers
The binding energies predicted by the Liquid Drop Model underestimate the actual
binding energies of “magic nuclei” for which either the number of neutrons
N = (A − Z) or the number of protons, Z is equal to one of the following “magic
numbers” 2, 8, 20, 28, 50, 82, 126. This is particularly the case for “doubly magic”
nuclei in which both the number of neutrons and the number of protons are equal
to magic numbers.
For example for 56Ni28 (nickel) the Liquid Drop Model predicts a binding energy of
477.7MeV, whereas the measured value is 484.0 MeV. Likewise for 132Sn50 (tin)
the Liquid Drop model predicts a binding energy of 1084 MeV, whereas the
measured value is 1110 MeV. There are other special features of magic nuclei:
The neutron (proton) separation energies (the energy required to remove the
last neutron (proton)) peaks if N (Z) is equal to a magic number.
There are more stable isotopes if Z is a magic number, and more stable
isotones if N is a magic number.
If N is magic number then the cross-section for neutron absorption is much
lower than for other nuclides.
The energies of the excited states are much higher than the ground state if
either N or Z or both are magic numbers.
Elements with Z equal to a magic number have a larger natural abundance
than those of nearby elements.
9.3
9.3The
TheShell
ShellTheory
TheoryPotential
Potential
The first step will be to identify a suitable average potential for the nucleons. One
obvious difference distinguishing nuclei from atoms is that the Coulomb potential
is not going to hack it. In the electron structure of an atom the electrons repel each
other, and the only reason the atom stays together is that there is a nucleus to
attract the electrons. But inside a nucleus, the nucleons all attract each other and
167
there is no additional attractive core. Indeed, a Coulomb potential like the one used
for the electrons in atoms would get only the first magic number, 2, right,
predicting 10, instead of 8, total particles for a filled second energy level.
A better potential is needed. Now in the center of a nucleus, the attractive forces
come from all directions and the net force will be zero by symmetry. Away from
the center, the net force will be directed inwards towards the center to keep the
nucleons together inside the nucleus. The simplest potential that describes this is
the harmonic oscillator one. For that potential, the inward force is simply
proportional to the distance from the center. That makes the potential energy
proportional to the square distance from the center, as sketched in figure (a).
Figure 5 (a) harmonic oscillator, (b) impenetrable surface, (c) Woods-Saxon,
(d) Woods-Saxon for protons.
The energy eigenvalues of the harmonic oscillator are
En ( n 1 / 2) , n=1,2,3...
Also, in spherical coordinates the energy eigenfunctions of the harmonic oscillator
can be taken to be of the form,
nlm Rnl ( r )Ylm ( , )
Here l is the azimuthal quantum number that gives the square orbital angular
momentum of the state as l (l 1) 2 ; m is the magnetic quantum number that gives
the orbital angular momentum in the direction of the arbitrarily chosen z-axis
as mh, and ms is the spin quantum number that gives the spin angular momentum
of the nucleon in the z-direction as msh. The spin up state with ms=1/2 is
commonly indicated by a postfix , and similarly the spin-down one ms=1/2 by .
Compared to the Coulomb potential of the hydrogen electron, the major difference
is in the number of energy states at a given energy level n. While for the Coulomb
potential the azimuthal quantum number l can have any value from 0 to n-1, for the
168
harmonic oscillator l must be odd or even depending on whether n-1 is odd or
even.
It does not make a difference for the lowest energy level n=1; in that case only l= 0
is allowed for either potential. And since the number of values of the magnetic
quantum number m at a given value of l is 2l+1, there is only one possible value
for m. That means that there are only two different energy states at the lowest
energy level, corresponding to ms=1/2 respectively -1/2. Those two states explain
the first magic number, 2. Two nucleons of a given type can occupy the lowest
energy level; any further ones of that type must go into a higher level.
In particular, helium-4 has the lowest energy level for protons completely filled
with its two protons, and the lowest level for neutrons completely filled with its
two neutrons. That makes helium-4 the first doubly-magic nucleus. It is just like
the two electrons in the helium atom completely fill the lowest energy level for
electrons, making helium the first noble gas.
At the second energy level n=2, where the Coulomb potential allows both l= 0
and l= 1, only l= 1 is allowed for the harmonic oscillator. So the number of states
available at energy level n- 2 is less than that of the Coulomb potential. In
particular, the azimuthal quantum number l= 1 allows 2l+1= 3 values of the
magnetic quantum number m, times 2 values for the spin quantum number ms.
Therefore, l= 1 at n= 2 corresponds to 3 times 2, or 6 energy states. Combined with
the two l= 0 states at energy level n=1, that gives a total of 8. The second magic
number 8 has been explained! It requires 8 nucleons of a given type to fill the
lowest two energy levels.
It makes oxygen-16 with 8 protons and 8 neutrons the second doubly-magic
nucleus. Note that for the electrons in atoms, the second energy level would also
include two l= 0 states. That is why the second noble gas is neon with 10 electrons,
and not oxygen with 8.
Before checking the other magic numbers, first a problem with the above
procedure of counting states must be addressed. It is too easy. Everybody can
evaluate 2l+1 and multiply by 2 for the spin states! To make it more challenging,
physicists adopt the so-called spectroscopic notation in which they do not tell you
the value of l. Instead, they tell you a letter like maybe p, and you are then
supposed to figure out yourself that l= 1. The scheme is:
169
The latter part is mostly alphabetic, but by convention j is not included. Using
spectroscopic notations, the second energy level states are denotated as
where the 2 indicates the value of n giving the energy level. The additional
dependence on the magnetic quantum numbers m and ms is kept hidden from the
uninitiated.
In these terms, the energy levels and numbers of states for the harmonic oscillator
potential are as shown in figure. The third energy level has 2 3s states and 10 3d
states. Added to the 8 from the first two energy levels, that brings the total count to
20, the third magic number.
Unfortunately, this is where it stops. The fourth energy level should have only 8
states to reach the next magic number 28, but in reality the fourth harmonic
170
oscillator level has 6 4p states and 14 4f ones. Still, getting 3 magic numbers right
seems like a good start.
The logical next step is to try to improve upon the harmonic oscillator potential. In
an average nucleus, it can be expected that the net force on a nucleon pretty much
averages out to zero everywhere except in a very thin layer at the outer surface.
The reason is that the nuclear forces are very short range; therefore the forces seem
to come equally from all directions unless the nucleon is very close to the surface.
Only right at the surface do the particles experience a net inward attraction because
of the deficit of particles beyond the surface to provide the full compensating
outward force. This suggests a picture in which the nucleons do not experience a
net force within the confines of the nucleus. However, at the surface, the potential
ramps up very steeply. As an idealization the potential beyond the surface can be
taken infinite.
That reasoning results in the impenetrable-shell. It too is analytically solvable, The
energy levels are shown in figure. Unfortunately, it does not help any explaining
the fourth magic number 28.
It turns out that once again the Saxon-Woods model is a reasonable guess, i.e.
V0
V ( r)
1 exp(( r R ) / )
Unfortunately, the fourth magic number remains unexplained. In fact, any
reasonable spherically symmetric spatial potential will not get the fourth magic
number right.
9.4Allowed
9.4 AllowedOrbits
OrbitsininthetheShell
ShellTheory
TheoryPotential
Potential
Eventually, Mayer in the U.S., and independently Jensen and his co-workers in
Germany, concluded that spin had to be involved in explaining the magic numbers
above 20. To understand why, consider the six 4p and fourteen 4f energy states at
the fourth energy level of the harmonic oscillator model. Clearly, the six 4p states
cannot produce the eight states of the energy shell needed to explain the next
magic number 28. And neither can the fourteen 4f states, unless for some reason
they split into two different groups whose energy is no longer equal.
171
Why would they split? In nonquantum terms, all fourteen states have orbital and
spin angular momentum vectors of exactly the same lengths. What is different
between states is only the direction of these vectors. And the absolute directions
cannot be relevant since the physics cannot depend on the orientation of the axis
system in which it is viewed. What it can depend on is the relative alignment
between the orbital and spin angular momentum vectors. This relative alignment is
characterized by the dot product between the two vectors.
Therefore, the logical way to get an energy splitting between states with differently
aligned orbital and spin angular momentum is to postulate an additional
contribution to the Hamiltonian of the form
H L. S
Here L is the orbital angular momentum vector and S the spin one. A contribution
to the Hamiltonian of this type is called an spin-orbit interaction, because it
couples spin with orbital angular momentum. Spin-orbit interaction was already
known from improved descriptions of the energy levels of the hydrogen atom.
However, that electromagnetic effect is far too small to explain the observed spin-
orbit interaction in nuclei. Also, it would get the sign of the correction wrong for
neutrons.
While nuclear forces remain incompletely understood, there is no doubt that it is
these much stronger forces, and not electromagnetic ones, that provide the
mechanism. Still, in analogy to the electronic case, the constant of proportionality
is usually taken to include the net force on the nucleon and an additional factor
1/r to turn orbital momentum into velocity. None of that makes a difference for the
harmonic oscillator potential, for which the net effect is still just a constant. Either
way, next the strength of the resulting interaction is adjusted to match the
experimental energy levels.
However, consider the net angular momentum operator
J=L+S
If you expand its square magnitude
J 2 ( L S ).( L S ) L2 2 L.S S 2
you see that the spin-orbit term can be written in terms of the square magnitudes of
orbital, spin, and net angular momentum operators:
172
1
L.S [ J 2 L2 S 2 ]
2
Therefore combination states that have definite square net angular
momentum J2 remain good energy eigenfunctions even in the presence of spin-
orbit interaction.
Now a quick review is needed of the weird way in which angular momenta
combine into net angular momentum in quantum mechanics. In quantum
mechanics, the length of the final vector must be quantized as j( j 1) where
the quantum number j must satisfy | l s | j | l s | and must change in integer
amounts. In particular, since the spin is given as s=1/2, the net angular momentum
quantum number j can either be l-1/2 or l+1/2. (If l is zero, the first possibility is
also ruled out, since square angular momentum cannot be negative.)
For the 4f energy level l= 3, so the square net angular momentum quantum
number j can only be 5/2 or 7/2. And for a given value of j, there are 2j+1, values
for the quantum number mj giving the net angular momentum in the chosen z-
direction. That means that there are six states with j=5/2 and eight states
with j=7/2. The total is fourteen, still the same number of independent states at the
4f level. In fact, the fourteen states of definite net angular momentum j can be
written as linear combinations of the fourteen states. Pictorially,
where the spectroscopic convention is to show the net angular momentum j as a
subscript for states in which its value is unambiguous. The spin-orbit interaction
raises the energy of the six 4f5/2 states, but lowers it for the eight 4f7/2 states. In
fact, from above, for any state of definite square orbital and square net angular
momentum,
2
L.S [ j ( j 1) l (l 1) s ( s 1)]
2
1 1
2 l ( l 1) 2
for j l -
2
=
1 l 2 for j l -
1
2 2
173
The eight 4f7/2 states of lowered energy form the shell that is filled at the fourth
magic number 28.
Figure 6 Schematic effect of spin-orbit interaction on the energy levels. The
ordering within bands is realistic for neutrons. The designation behind the
equals sign is the official one.
Figure shows how the spin-orbit splitting of the energy levels gives rise to the
remaining magic numbers. In the figure, the coefficient of the spin orbit term was
simply taken to vary linearly with the energy level n. The details depend on
whether it is neutrons or protons, and may vary from nucleus to nucleus. Especially
for the higher energy bands the Coulomb repulsion has an increasingly large effect
on the energies of protons.
The major shells, terminated by magic numbers, are shown as grey bands. In the
numbering system followed here, a subshell with a different number as the others
in the same major shell comes from a different harmonic oscillator energy level.
174
9.5
9.5Self
SelfLearning
LearningExercise-I
Exercise-I
Q.1 Write down top five magic numbers
Q.2 Draw Woods Saxon potential for protons.
Q.3 What is spin orbit coupling?
Q.4 Write down draw backs of Liquid drop model.
9.6
9.6Filling
FillingofofthetheOrbits
OrbitsininthetheShell
Shelltheory
theoryPotential
Potential
Nuclear states have an intrinsic spin and a well defined parity, p=±1, defined by
the behaviour of the wavefunction for all the nucleons under reversal of their
coordinates with the centre of the nucleus at the origin.
( r1 , r2 ,... rA ) p ( r1 , r2 ,...rA )
The spin and parity of nuclear ground states can usually be determined from the
shell model. Protons and neutrons tend to pair up so that the spin of each pair is
zero and each pair has even parity (p = 1). Thus we have
• Even-even nuclides (both Z and A even) have zero intrinsic spin and even
parity.
• Odd A nuclei have one unpaired nucleon. The spin of the nucleus is equal to
the j value of that unpaired nucleon and the parity is (−1)l, where l is the
orbital angular momentum of the unpaired nucleon.
Example 47Ti22 (titanium) has an even number of protons and 25 neutrons. 20 of the
neutrons fill the shells up to magic number 20 and there are 5 in the 1f7/2 state (l =
3, j = 7/2 ) Four of these form pairs and the remaining one leads to a nuclear spin
of 7/2 and parity (−1)3 = −1.
• Odd-odd nuclei. In this case there is an unpaired proton whose total angular
momentum is j1 and an unpaired neutron whose total angular momentum is j2.
The total spin of the nucleus is the (vector) sum of these angular momenta and
can take values between |j1 − j2| and |j1 + j2| (in unit steps). The parity is given
by (−1)(l1+l2), where l1 and l2 are the orbital angular momenta of the unpaired
proton and neutron respectively.
Example 6Li3 (lithium) has 3 neutrons and 3 protons. The first two of each fill the
1s level and the third is in the 1p3/2 level. The orbital angular momentum of each
175
is l = 1 so the parity is (−1)×(−1) = +1 (even), but the spin can be anywhere
between 0 and 3.
9.7
9.7Magnetic
MagneticDipole
DipoleMoments
Moments
Since nuclei with an odd number of protons and/or neutrons have intrinsic spin
they also in general possess a magnetic dipole moment.
The unit of magnetic dipole moment for a nucleus is the “nuclear magneton”
defined as
e
N
2mP
which is analogous to the Bohr magneton but with the electron mass replaced by
the proton mass. It is defined such that the magnetic moment due to a proton with
orbital angular momentum l is μ l.
Experimentally it is found that the magnetic moment of the proton (due to its spin)
is
μp = 2.79μN = 5.58μNs, (s =1/2)
and that of the neutron is
μn = −1.91μN = −3.82μNs, (s =1/2)
If we apply a magnetic field in the z-direction to a nucleus then the unpaired proton
with orbital angular momentum l, spin s and total angular momentum j will give a
contribution to the z− component of the magnetic moment
μz = (5.58sz + lz) μN.
As in the case of the Zeeman effect, the vector model may be used to express this
as
(5.58 s. j l. j )
z 2
j z N
j
Using j 2 j( j 1)2
1
s. j ( j 2 s 2 l 2 )
2
176
2
= [ j ( j 1) s ( s 1) l (l 1)]
2
1
l. j ( j 2 l 2 s 2 )
2
2
= [ j ( j 1) l ( l 1) s ( s 1)]
2
We end up with expression for the contribution to the magnetic moment
(5.58[ j ( j 1) s( s 1) l (l 1)] [ j ( j 1) l ( l 1) s ( s 1)])
z jN
2 j ( j 1)
and for a neutron with orbital angular momentum l′ and total angular momentum j′
we get (not contribution from the orbital angular momentum because the neutron is
uncharged)
(5.58[ j`( j `1) s`( s`1) l `( l `1)]
z j` N
2 j`( j`1)
Thus, for example if we consider the nuclide 7Li3 for which there is an unpaired
proton in the 2p3/2 state (l = 1, j = 3/2 then the estimate of the magnetic moment is
μ =3.79μN
The measured value is 3.26μN so the estimate is not too good. For heavier nuclei
the estimate from the shell model gets much worse.
The precise origin of the magnetic dipole moment is not understood, but in general
they cannot be predicted from the shell model. For example for the nuclide 17 F9
(fluorine), the measured value of the magnetic moment is 4.72μN whereas the
value predicted form the above model is −0.26μN. There are contributions to the
magnetic moments from the nuclear potential that is not well-understood.
9.8
9.8Shell
ShellModel
ModelFailures
Failures
1. Excited States:
As in the case of Atomic Physics, nuclei can be in excited states, which decay via
the emission of a photon ( gamma ray) back to their ground state (either directly or
indirectly). Some of these excited states are states in which one of the neutrons or
protons in the outer shell is promoted to a higher energy level.
177
However, unlike Atomic Physics, it is also possible that sometimes it is
energetically cheaper to promote a nucleon from an inner closed shell, rather than a
nucleon form an outer shell into a high energy state. Moreover, excited states in
which more than one nucleon is promoted above its ground state is much more
common in Nuclear Physics than in Atomic Physics.
Thus the nuclear spectrum of states is very rich indeed, but very complicated and
cannot be easily understood in terms of the shell model. Most of the excited states
decay so rapidly that their lifetimes cannot be measured. There are some excited
states, however, which are metastable because they cannot decay without violating
the selection rules. These excited states are known as “isomers”, and their lifetimes
can be measured.
2. Imperfect Pairing:
In case of titanium-47, the shell model predicts that there will be five neutrons in
an unfilled 4f7/2 subshell. It is believed that this is indeed correct. The unperturbed
shell model makes no predictions about the nuclear spin. However, the odd-particle
shell model says that in the ground state the nuclear spin should be that of the odd
neutron, 7/2. But it is not, the spin is 5/2. The pairing of the even number of
neutrons in the 4f7/2 shell is not complete. While unfortunate, this is really not that
surprising. The perturbation Hamiltonian used to derive the prediction of nucleon
pairing is a very crude one. It is quite common to see subshells with at least three
particles and three holes (three places for additional particles) end up with a unit
less spin than the odd-particle model predicts. It almost happened for oxygen-19.
3. Wrong Shell:
Fluorine-19 shows a more fundamental failure of the shell model. The shell model
would predict that the odd proton is in the 3d5/2 state, giving the nucleus
spin 5/2 and even parity. In fact, it should be just like fluorine-17. For the
unperturbed shell model, the additional two neutrons should not make a significant
difference. But the nuclear spin is1/2, and that means that the odd proton must be
in the 3s1/2 state. Which show that the unperturbed shell model cannot
qualitatively explain this swapping of the two states.
It is the theoretician’s loss, but the experimentalist’s gain. The fact that fluorine has
spin one-half makes it a popular target for nuclear magnetic resonance studies.
178
Spin one-half nuclei are easy to analyze and they do not have nontrivial electric
fields that mess up the nice sharp signals in nuclei with larger spin.
And maybe the theoretician can take some comfort in the fact that this complete
failure is rare among the light nuclei. In fact, the main other example is fluorine-
19’s mirror twin neon-19. Also, there is an excited state with the correct spin and
parity just above the ground state. But no funny business here; if you are going to
call fluorine-19 almost right, you have to call fluorine-17 almost wrong.
Note also how low the ½- excited state has become. Maybe this can be somewhat
understood from the fact that the kicked-up 2p1/2 proton is now in a similar spatial
orbit with three other nucleons, rather than just one like in the case of fluorine-17.
In any case, it would surely require a rather sophisticated perturbed shell model to
describe it, one that includes nucleons of both type in the perturbation.
And note that formulating a perturbed shell model from physical principles is not
easy anyway, because the basic shell model already includes the interactions
between nucleons in an average sense. The perturbations must not just identify the
interactions, but more importantly, what part of these interactions is still missing
from the unperturbed shell model.
4. Promotion:
Selenium-77 illustrates a more fundamental reason why the odd particle may end
up in the wrong state. The final odd neutron would normally be the third one in the
5g9/2 state. That would give the nucleus a net spin of 9/2 and positive parity. There
is indeed a low-lying excited state like that. (It is just above a 7/2 one that might be
an effect of incomplete pairing.) However, the nucleus finds that if it promotes a
neutron from the 4p1/2 shell to the 5g9/2 one just above, that neutron can pair up at
higher angular momentum, lowering the overall nuclear energy. That leaves the
odd neutron in the 4p1/2 state, giving the nucleus a net spin of 1/2 and negative
parity. Promotion happens quite often if there are more than 32 nucleons of a given
type and there is a state of lower spin immediately below the one being filled.
5. Non spherical nucleus:
Tantalum-181 is an example nucleus that is not spherical. For it, the shell model
simply does not apply as derived here. So there is no need to worry about it. Which
is a good thing, because it does not seem easy to justify a 7/2+ ground state based
179
on the shell model. Nonspherical nuclei appear near the stable line for mass
numbers of about 150 to 190 and above 220. There are also a few with mass
numbers between 20 and 30.
Preston & Bhaduri give an extensive table of nucleons with odd mass number,
listing shell occupation numbers and spin. Notable is iron-57, believed to have
three neutrons in the 4p3/2 shell as the shell model says, but with a net nuclear spin
of ½-. Since the three neutrons cannot produce that spin, in a shell model
explanation the 6 protons in the 4f7/2 shell will need to contribute. In general the
table shows that the ground state spin values of spherical nuclei with odd mass
numbers are almost all correctly predicted if you know the correct occupation
numbers of the shells. However, predicting those numbers for heavy nuclei is often
nontrivial.
9.9
9.9Self
SelfLearning
LearningExercise-II
Exercise-II
Q.1 Calculate magnetic moment of 7Li3
Q.2 What is a “halo nucleus,”
Q.3 Give the spin and parity, as expected from the shell model, of the ground
states of 173Yb.
Q.4 Write a short note on “Failures of nuclear shell model”
9.10Summary
9.10 Summary
The unit starts with the introduction of Nuclear models followed by a detailed
discussion of nuclear shell model.
9.11Glossary
9.11 Glossary
Angular Momentum : A measure of the momentum of a body in rotational
motion about its centre of mass. Technically, the angular momentum of a body is
equal to the mass of the body multiplied by the cross product of the position vector
of the particle with its velocity vector. The angular momentum of a system is the
sum of the angular momenta of its constituent particles, and this total is conserved
unless acted on by an outside force.
Neutron : One of the two main building blocks (along with the proton) of the
nucleus at the centre of an atom. Neutrons have essentially the same mass as a
proton (very slightly larger) but no electric charge, and are made up of one “up”
180
quark and two “down” quarks. The number of neutrons in an atom determines the
isotope of an element. Outside of a nucleus, they are unstable and disintegrate
within about ten minutes.
Nucleus : The tight cluster of nucleons (positively-charged protons and zero-
charged neutrons, or just a single proton in the case of hydrogen) at the centre of an
atom, containing more than 99.9% of the atom’s mass. The nucleus of a typical
atom is about 100,000 smaller than the total size of the atom(depending on the
individual atom).
Proton : One of the two main building blocks (along with the neutron) of the
nucleus at the centre of an atom. Protons carry a positive electrical charge, equal
and opposite to that of electrons, and are made up of two “up” quarks and one
“down” quark. The number of protons in an atom’s nucleus determines its atomic
number and thus which chemical element it represents.
Spin : Spin is a characteristic property of elementary particles
9.12
9.12Answers
AnswerstotoSelf
SelfLearning
LearningExercises
Exercises
Answers to Self Learning Exercise-I
Ans.1: 2, 8, 20, 28, 50
Ans.3: H L.S
Here L is the orbital angular momentum vector and S the spin one. A
contribution to the Hamiltonian of this type is called an spin-
orbit interaction, because it couples spin with orbital angular momentum.
Ans.4: See Section 9.2
Answers to Self Learning Exercise-II
Ans.1: μ =3.79μN
Ans.2: A nucleus whose radius is noticeably larger than that predicted by the
liquid drop formula.
Ans.3: 5/2-
9.13Exercise
9.13 Exercise
Q.1 Give the spin and parity, as expected from the shell model, of the ground
181
states of
7Li, 5N, 29Si, 43Ca, 87Ru, 133Cs.
Q.2 Write down a short note on nuclear shell model.
Referencesand
References andSuggested
SuggestedReadings
Readings
1. Concepts of Nuclear Physics by Bernard L. Cohen, 1971
2. Introductory Nuclear Physics, by K.S. Krane, 1988.
3. Structure of the Nucleus by M.A. Preston and R.K. Bhaduri,1975.
4. Theory of Nucleus. By A. Sitenko and V. Tartakovskii,1997.
5. The shell model Nobel Lecture by Maria Goeppert Mayer,1963.
182
UNIT-10
Beta Decay
Structure of the unit
10.0 Objectives
10.1 Introduction
10.2 General characteristics of weak interaction.
10.3 Nuclear Beta decay and lepton capture
10.4 Energy Consideration in , and EC reactions.
10.5 Fermi theory of beta decay
10.6 Electron energy spectrum and Fermi Kurie plot
10.7 Parity conserved selection rules for Fermi and Gamow Teller Transitions
10.8 f t values and forbidden Beta transitions
10.9 Experimental verification of parity violation
10.10 V−A Theory of Fermi beta decay with parity conserving and
nonconserving terms.
10.11 Summary
10.12 Glossary
10.13 Exercise
10.14 Answers to Exercise
References and Suggested Readings
10.0
10.0Objectives
Objectives
The nucleus decays through various forms of decay : , and electron capture.
The reader learn about allowed and forbidden beta transitions and f t –values.
Fermi and Gamow Teller transitions are explained so that the student can
differentiate between two types of transitions .V−A theory of beta decay is
introduced so that the reader learns the concept of parity violation in the context of
beta decay process.
183
10.1
10.1Introduction
Introduction
The decay processes falling under beta decay category are described with proper
theoretical models using concepts and tools of quantum mechanics and quantum
field theory. The Fermi Kurie plot and parity non conservation are deduced from
the theoretical (phenomenological ) models. The concept of f t values and Fermi
and Gamow –Teller transitions are introduced to understand the experimental
observations .The better comprehension of beta decay processes comes from
recognition of the role of weak interaction in the phenomena.
10.2
10.2General
GeneralCharacteristics
CharacteristicsofofWeak
WeakInteraction
Interaction
Nuclear beta decay is only one class of phenomena out of many other classes of
phenomena occurring due to weak interaction .The weak interaction not only
produces transitions between nuclear states but a wide categories of phenomena
involving leptons, mesons, hadrons etc. The weak processes cannot be observed
because these are slower by several orders of magnitude compared with competing
electromagnetic and strong processes. The studies of weak processes can be made
in the areas where faster electromagnetic and strong processes are forbidden and
suppressed by selection rules.
Let us consider the basic weak reactions in nuclei which produce nuclear
transitions .
The decay of a free neutron and a bound proton are
n p e e (10.1)
and pbound n e e (10.2)
The decay of hadrons ,for example
(10.3)
e e
(10.4)
e e
n (10.5)
184
o
(10.6)
The decay of nucleons [given by eq.(10.1) and (10.2)] and decay of hadrons [given
by eq.(10.3) and (10.4)] are called semi- leptonic processes as these processes
involve leptons also.
The decay of hadrons without any lepton are called non leptonic processes [given
by eq.(10.5) and (10.6)].
The decay of leptons are ,for example ,
e e (10.7)
This is pure leptonic process.
Now it is clear that weak processes are of three types: pure leptonic ,semi leptonic
and non leptonic and non leptonic .Beta decay is basically semi leptonic nucleon
decays causing nuclear transitions and an integral part of weak processes.
We will now consider the general characteristics of weak interaction processes.
(i) Universal Strength:
The weak interaction exhibits the same interaction strength in all types of the
processes like pure leptonic , semi leptonic and non leptonic processes. This
universal weak coupling constant , designated by Fermi coupling constants, has the
same value.
GF 1.43584 0.00003 1062 J m3
3 2
1.166637 0.00002 1011 c MeV (10.8)
whether it is measured through super allowed -decay in nuclei or from
muon decay or from other weak processes.
(ii) W ,W and Z o Vector Bosons are Weak Interaction Carriers:
The vector Bosons carry the weak interaction as photons carry electromagnetic
interaction. The masses of the vector bosons are
MW c 2 80.9 1.4 GeV
(10.9)
M Z o c 2 91.9 1.8 GeV
185
(iii) Range of weak interaction is very short ( 103 fm ):
The characteristic range of the weak interaction can be calculated using
Heisenberg’s uncertainty relation
c
r pc (10.10)
2
and taking Mc 2 100 GeV as typical mass of weak vector boson ,we get
c 200MeV fm
r 103 fm (10.11)
2Mc 2 2 100GeV
We see that range of the weak interaction is approximately three orders of
magnitude smaller than long range of the nuclear force (103 times smaller).
(iv) SU3 Flavour Symmetry Mixing:
Fundamentally , beta decay may be viewed as one type of quark transformed into
another through exchange of charged vector boson. In general one type of particle
(quark or lepton) changes into another particle through exchange of W and Z o in
the weak interaction processes .When a quark decays into another quark, it does
not necessarily have a definite flavour i.e. it may result in Flavour Mixing.
The customary Transformation for weak decay among four quarks u,d,c and s can
be expressed in terms of the Cabbibo angle , c
cos c sin c d
jweak u c (10.12)
sin c cos c s
The more general case of the transformation for weak decay among all six quarks
u,d,c,s,t and b can be expressed using the 3×3 Kobayashi –Maskawa matrix:
M 11 M 12 M 13 d
jweak u c t M 21 M 22 M 23 s (10.13)
M 31 M 32 M 33 b
The nine matrix elements are functions of three mixing angles and a phase factor.
In the nuclear beta decay ,we are concerned with transformation between u and d
quarks. Let us view (10.1) and (10.2) decays in terms of quark weak
transformations:
186
n p e e
u d d u u d W
e e
d u W
(10.14)
e e
p n e e
u u d u d d W
e e
u d W
(10.15)
e e
The Feynman diagrams for and decays are shown in figure (10.1) and figure
(10.2).
e
e
d
u e
e
W W
u
d
Figure 10.1: decay Figure 10.2: decay
(v) Parity Nonconservation:
The parity transformation is the operation which inverts the spatial coordinates and
physically described as taking mirror image of the coordinate system. The parity of
a particle (Fermion) and its antiparticle (Fermion) are opposite to each other .The
parity of π is taken as negative. The formal definition of parity operator P is given
as
P r r r (10.16)
Here + sign corresponds to positive parity (even) while – sign refers to negative
parity (odd) of the function r .If a function does not fall into any of these two
categories is said to have nondefinite parity .It is helpful to consider the parity of
following type of nature of operators/functions:
187
S.No. Type of operator / Function Symbol Parity
1. Usual vector/Polar vector V Odd
(example: r , p )
2. Axial Vector A Even
Example: L,S ,r p
3. Scalar S Even
Example: density ,numerical constants like e,1,π; dot
product of two axial vectors or of two polar vectors
4. Pseudo Scalar P Odd
Examples: Scalar product of an axial and a polar
vector
Now let us consider the angular distribution of electrons emitted in decay with
given momentum p ; energy E and spin , denoted by W .The expression for
W is given by
.p
W 1 a
E
v
W 1 a cos (10.17)
c
where : angle of electron emission between momentum p and its angular
momentum J .
The first term is a scalar while the second is a pseudo scalar in eq.(10.17) and if
a≠ 0 ,then these two terms will behave differently under parity operation. It will
lead to different angular distribution under spatial coordinate inversion and parity
60
violation of W .The experimental measurement of W in the 27 Co nucleus
decay experiment carried out by Wu and others confirmed this strange
conclusion .The existence of two decay modes of K in nature (10.6) (final states
having two and three pions) also confirmed parity nonconservation in weak
interactions. Hence parity non conservation is a basic characteristic of weak
processes.
188
10.3
10.3Nuclear
NuclearBeta
BetaDecay
Decayand
andLepton
LeptonCapture
Capture
The nuclei ,which lie above the stability region ,emit electrons ,antineutrinos and
daughter nuclei with same mass number A remain as residual nuclei, but atomic
number increased by unity. In decay ,a neutron is replaced by/transformed into
a proton ,and parent and daughter nuclei are isobars consequently.
The process can be expressed as :
A
Z
X Z A1Y e e (10.18)
The more precise expression can be written as
1
0
n 11 p 10e 00 e (10.18a)
The following observations can be expressed explicitly
(i) X and Y are isobars. Nucleons are conserved ;A=A.
(ii) Electric charge is conserved ; 0 1e 1e 0 0
(iii) Intrinsic spin is conserved
(iv) Leptons are conserved.
For Example
14
6
C 147 N e e (10.18 b)
14
6
C is a emitter.
Similarly ,for decay ,the process can be expressed as
A
Z
X Z A1Y e e (10.19)
The more precise expression can be written as
p n e e (10.19a)
The following observations can be made explicitly
(i) X and Y are isobars.Nucleons are conserved ; A=A
(ii) Leptons are conserved; 0 1 1
(iii) Electric charge is conserved; 1e 1e
(iv) Intrinsic spin is conserved.
189
We can take following Example
11
6
C 11
5
B e e (10.19b)
11
6
C is a emitter.
Similarly ,for electron capture (E C),the process can be expressed as
A
Z
X e Z A1Y e (10.20)
The more precise expression can be written as
p e n e (10.20a)
Again , following observations can be made explicitly
(i) X and Y are isobars.Nucleons are conserved; A=A
(ii) Electric charge is conserved; 1e 1e 0 0 0
(iii) Leptons are conserved.
(iv) Intrinsic spin is conserved.
We take another example as
7
4
Be e 37 Li e (10.20b)
T1/ 2 53.4d ,Q 0.86 MeV
Special Note :Positron e was theoretically predicted by Dirac (1927) and
experimentally verified by Anderson (1932).
10.4
10.4 Energy
Energy Consideration
Consideration in ,, and Electron
and Electron Capture
Capture
Reactions
Reactions
Let us consider the relation between the atomic mass and the nuclear mass.
M Z , A N Z , A Zme BZ (10.21)
M * Z ,A N Z ,A Zme B*Z K P,... (10.21a)
where
M Z ,A mass of the atom Z ,A in ground state
me mass of the free electron
190
N Z ,A mass of the nucleus Z ,A in ground state
BZ : Binding energy of all orbiting electrons of atom M Z ,A in ground state.
Z
bi
i 1
M * Z ,A :mass of the atom Z ,A in excited state {hole- particle pair h p pair }
B*Z K P : Binding energy of all orbiting electrons of atom in M * Z ,A in
excited state h p pair
Z
bi bP bK
i 1
BZ ph (10.22)
electron p
hole h
The difference in binding energy BZ of Z orbiting electrons of the atom M Z ,A
and the binding energy BZ 1 of Z 1 electrons of the atom M Z 1,A
is very small. The difference is B 10 50 keV typically.
B
The masses M Z ,A , N Z ,A and me are the order of MeV. The ratio in
M
processes is of the order of 0.1% or less.
The Q value for decay:
A
Z
X Z A1Y e e
n p e e is given as
Q N Z N Z 1 me (10.23)
If we change nuclear masses into atomic masses then
Q M Z BZ Zme M Z 1 BZ 1 Z 1 me me
Q M Z BZ M Z 1 BZ 1 (10.24)
191
The Q value for decay:
A
Z
X Z A1Y e e
p n e e is given as:
Q N Z N Z 1 me (10.25)
Changing nuclear masses into atomic masses ,we can rewrite above relation as
Q M Z BZ Zme M Z 1 BZ 1 Z 1 me me
Q M Z BZ M Z 1 BZ 1 2me (10.26)
The Q value for EC
A
Z
X e Z A1Y e
p e n e is given as
e
QEC N Z m N Z 1 b Z K (10.27)
e
where b Ze K : binding energy of K electron. Changing nuclear masses into atomic
masses ,we can rewrite above relation
QEC M Z M *Z 1 (10.28)
e
QEC M Z BZ M Z 1 BZ 1 b Z K
Hence we notice that EC (electron capture) decay demands that mass difference of
parent- daughter must be at least greater than or equal to binding energy of K or L
or any other shell. The Q value in this case is sum of kinetic energy of daughter
nucleus and neutrino.
10.5
10.5Fermi
FermiTheory
TheoryofofBeta
BetaDecay
Decay
In the beta decay a nucleon changes into another type of nucleon and electron
(positron) and antineutrino (neutrino) are created. Fermi assumed parity
conservation but his calculations involved only scalar quantities .The results of his
theory still stand in large measure, inspite of the fundamental changes produced by
the parity violation.
192
The theory explained:
(1) Form of beta spectra : Number of electrons in beta process/energy interval
dN e
versus energy of electron Ee .
dEe
(2) The relation between maximum energy of beta decay and mean life time.
(3) The classification of beta transitions and establishment of selection rules.
The transition probability for beta transition is given by Golden Rule of time
dependent perturbation theory:
2 2
H
if
g Ef (10.29)
where
Hif Matrix element of beta interaction
g E f Density of final energy states of final products of beta process
Probability of transition
The relation is applicable because universal Fermi coupling constant GF and
universal vector coupling constant GV are very small.
Let us consider the transition
A
Z
X Z A1Y e1 e
n p
e e
Then f Y e
e
i X (10.30)
Now Fermi assumed the form of interaction
Hˆ GV M
ˆ (10.31)
where GV 1.4029 0.0022 1062 Jm3
3 2
1.1396 0.0018 1011 c MeV
3
0.875 0.002 104 MeV fm
193
We have discussed GF earlier in equation (10.2).
The matrix element of beta process is
H if GV *Y *e * M X d (10.32)
e
Taking *
e e
H if GV *Y *e M X d
e
Let us consider parent nucleus X at rest ,then momentum conservation yields
PR Pe P PX 0 (10.33)
e
The energy conservation leads to
Eo ER Ee E (10.34)
e
Let us take the case when electron and neutrino are considered as a pair and the
nucleus and this pair share the momentum i.e.
PR max pe max 0 (10.35)
e
Then Eo ER max Ee (10.36)
e max
Eq.(10.35) and eq.(10.36) imply
PR max pe
e max
PR2max
E R max
2 A.M .
p 2e E 2emax me2c 4
e max
me
2 A.M . 2 A.M . mec 2
ER max
me E 2
e max
me2c 4 (10.37)
2 A.M . me c 2
where
A Mass number of daughter nucleus
me mass of electron emitted in decay
M Mass of a nucleon
194
ER max
The ratio can be evaluated as
Ee
e max
2 2 4
ER max m Ee max me c
e 2
Ee max 2 AM Eemax mec
Take the typical values
1
me MeV ,M 1000MeV , A 10 ,then
2
me 1
3 105 mec 2 MeV , Ee max 10 MeV
2 AM , 2
Ee2 max me2c 4
20
Ee max mec 2
ER max
Hence 60 105 103 (10.38)
Ee max
Hence we conclude that recoil energy can be neglected.
Now approximate energy momentum conservation relations can now be written
PR pe p 0
e
Ee E Eo (10.39)
e
The energy in decay process is shared by electron and neutrino effectively.
10.6
10.6Electron
ElectronEnergy
EnergySpectrum
Spectrumand
andFermi
FermiKurie
KuriePlot
Plot
Wavefunctions of anti neutrino and electron:
The neutrino interacts very weakly with nucleons and move with v c . It is,
therefore , reasonable to use plane wave free particle wavefunction
1 i p .r
e
e (10.40)
1/ 2
where volume of the box enclosing the system.
195
The electron interacts with nucleons but its velocity is very high, so we can neglect
the electromagnetic interaction. The electron wavefunction can also be taken as
plane wave free particle wavefunction:
e
1
e
i pe .r
(10.41)
1/ 2
Further
1 i pe pe .r
e e
e
2 3
1
i p e p .r
1 e
e
p e p .r i
p e p .r
e
....
22 63
Taking pe p mec , 2mec 2 1MeV ,R 10 fm
e
2mec 2 10 MeV fm 1
and R ,we get
c 200 MeV fm 20
2 3
1 1 1 1 i 1
e 1 i ...
e 20 2 20 6 20
1 1 2 1 1 1
1 .10 i .10 .103 ....
8 2 48
1
e (10.42)
e
We see that electron -neutrino field is weak in comparison to short range strong
interaction among nucleons. The decay process is analogous to emission of
electromagnetic radiation with electron -neutrino field in place of photon .This
makes the matrix element
GV *
H if Y M X d
196
GV
M if (10.43)
We assume that all partitions of energy E0 Ee E are equally probable. This
e
means that the transition probability of beta decay is proportional to the volume of
accessible phase space in that transition.
The number of states dN e corresponding to appearance in volume of electron
with momentum in pe and pe dpe range is :
4 2
dN e pe dpe (10.44)
h3
Similarly number of states dN corresponding to appearance in volume of
e
neutrino with momentum in p and p dp range is
e e e
4 2
dN p dp (10.45)
e h3 e e
Hence the number of states for electron -neutrino pair is given by
2
2 4 2 2
d N pe p e dpe dp e (10.46)
h3
For a fixed electron energy Ee , the relation
E0 E e E dE0 dE
e e
2
E2 E0 Ee
For neutrino e
p2
2 2 e
c c
E p c
e e
dE
e
dp (10.47)
c e
For electron
Ee2 pe2c 2 me2c 4
197
dEe
dpe (10.48)
c
Using eq. (10.47) and (10.48), we get dN as
2
2 4 2 2
d N pe p e dpe dp e
h3
2 2
2 4 2 E0 Ee dE0
d N 3 pe dpe c
(10.49)
h c
The density of states E0 can be written as
2
d 2N 1 4 2 2
dE0 c3 h3 pe E0 Ee dpe
2
1 4 2 2
E0 dpe
c 3 h3
pe E0 Ee dpe (10.50)
The probability of transition using eq.(10.29) employing Fermi Golden rule
2 2
pe dpe
H if E0 dpe
2 2
2 GV 2 1 4 2 2
2
M if p E Ee
c3 h3 e 0
dpe
2
2
1 GV M if 2
pe dpe
2 3 7 3
c
pe2 E0 Ee dpe (10.51)
2
2
1 GV M if 2
Ee dEe
2 3 7 c3
E0 Ee pe Ee dEe (10.52)
The M if is independent of pe and dp for allowed transitions. This fact
e
produces beta decay spectrum.
The plot between pe versus Ee is shown in figure.
198
keV / c
0.300 0.600 0.900
300
pe e
e
200
100
50 100 200 300 400 500 600
Ee keV
64
Fig10.3 : Momentum spectra for Cu electrons and positrons [Wu & Albert
(1949)]
1/ 2
p
Generally 2 e
versus Ee is plotted .It is straight line and called
p F Z ,E
e e
Fermi Kurie plot.
e
1/2
pe
2
pe F Z , Ee
e
100 200 300 400 500 570 600
Ee keV
64
Figure 10.4 : The Fermi Kurie plot of Cu beta spectra .End points are
571keV e and 657 keV e [Owen &Cook (1949)]
199
The departure from the straight line are attributed to a dependence of M if on pe
such as occurs in forbidden transitions according to eq.(10.41) and (10.42).
Coulomb Factor F Z ,Ee is defined as
2
e 0
F Z ,Ee Coulomb
2
(10.53)
e 0
free
Coulomb factor takes care of the fact that electrons are not really free but
interacting with nucleons (Coulomb interaction).
The corrected expression for (10.52) is
2
2
1 GV M if 2
pe dpe
2 3 7 c3
F Z ,Ee pe2 E0 Ee dpe
2
2
1 GV M if 2
Ee dEe
2 3 7 5
c
F Z ,Ee E0 Ee pe Ee dEe (10.54)
All momenta are expressed in terms of pe me c and all energies in terms of
Ee e mec 2 ,E0 0mec 2
We get above equations in unitless variables.
2 5 4
1 GV me c 2 2 2
d
2 3 7
M if
F Z ,e 0 e d
2
5 4
1 GV me c 2 2
e d e
2 3 7
M if
F Z ,e 0 e ed e (10.55)
The decay constant can be expressed as
2
0 M if 0
2 2
d 0 F Z ,e 0 e d (10.56)
0 0
2 5 4
1 1 GV me c
where (10.57)
0 2 3 7
0 Universal Time constant for beta process.
200
The estimate for 0 is
1
0 4
s 9.709 103 s 2.7hrs (10.58)
1.03 10
0
2
Taking F Z ,e 0 e 2d
f 0 (10.59)
0
can be expressed as
2
M if
0
f 0 (10.60)
Here we have defined
f 0 Coulomb Fermi Factor
From the decay law
t
N N0e (10.61)
We get half life as
2
ln 2 0.693 M if
t1/ 2
t1/ 2
0
f 0 (10.62)
We can write h p pair
6728s 1.9hrs
The product of Coulomb Fermi Factor and half life of nucleus for beta decay is
called comparative half life f t1/ 2 or usually written as ft.
10.7
10.7Parity
ParityConserved
ConservedSelection RulesRules
Selection for Fermi and Gamow
for Fermi and
Teller
Gamow Transitions
Teller Transitions
Selection Rules
Angular momentum conservation dictates
I f Ii L (Fermi Type)
I f Ii L ( Gamow Teller Type)
201
In the Fermi Type transitions emitted light particles have their spins antiparallel.
Singlet state e e S eZ S Z
But in the Gamow Teller type transitions emitted light particles have their spins
parallel.
Triplet state e e SeZ S Z
Parity changes are determined by
L
f i 1
The total orbital angular momenta carried by e ,e light particles is denoted by
L .
We assume that e ,e are emitted by the point nucleus.
R
1 hence k .r 0
e or
e
But if we consider
R
1 then
e or
e
e 0 / 1 but 1 ike .r ......
* 0
/ 1 but 1 ik .r ......
e e
The inclusion of k .r L 1
2
k .r
L 2
2
The wavefunctions should be considered in the volume rather than at the centre.
Relativistic consideration is required .
These modifications produce nonlinearity in Kurie plots and higher order
transitions occur for L 0 .
So we classify the transitions as
If L 0 allowed
202
L 1 Forbidden Ist Order
L 2 Forbidden 2nd Order
Transition L I (Fermi) I (G.T.) (G.T.)
(Fermi)
Allowed 0 0 No (0),1 No
First Forbidden 1 (0),1 Yes 0,1,2 Yes
Second Forbidden 2 (1),2 No 2,3 No
Third Forbidden 3 (2),3 Yes 3,4 Yes
Fourth Forbidden 4 (3),4 No 4,5 No
Those not possible ,if either Ii or If is zero, are in parenthesis.
The Gamow Teller transitions for which I L 1 only then these transitions are
called unique transitions or pure transitions.
The mixing of Fermi and Gamow Teller transitions changes the shape of Curie
plots.
General Selection rules
Fermi I n, n 1
n
f i 1
Gamow Teller I n, n 1
n
f i 1
10.8
10.8f ft tValues
Valuesand
andForbidden
ForbiddenBeta
BetaTransitions
Transitions
The allowed or forbidden nature of transitions is often determined from the
measurement of ft 1 2 values.
ft 1 2 value depends upon
Z
End point energy ε0
Half life t1/ 2
203
ft 1 2
has large variations so log10 ft 1 2 is considered
log10 ft 1 2 value Type of transition
2.7-3.7 Super allowed
4-5.8 allowed
6-10 First forbidden
10-14 Second Forbidden
14-17 Third Forbidden
17-24 Fourth Forbidden
We can take following examples:
Fermi type:
L 0 14
8
O 14
7
N* e e
0 0
L 1 87
Kr 87 Rb e e
5 3
2 2
111
Ag 111Cd e e
1 1
2 2
L 2 135
Cs 135 Bi e e
7 3
2 2
L 3 87
Rb 87 Sr e e
3 9
2
2
L 4 115
In 115 Sn e e
9 1
2 2
204
Gamow Teller type:
L 0 6
2
He 63 Li e e
0 1
L 1 37
S 37Cl e e
7 3
2 2
L 1 85
Kr 85 Rb e e
9 5
2 2
L 2 10
Be 10 B e e
0 3
L 2 22
Na 22 Ne e e
3 0
10.9
10.9Experimental
ExperimentalVerification
VerificationofofParity
ParityViolation
Violation
If the process and its parity reversed process both occur in nature with the same
probability ,then the process is said to be parity invariant.
e e
B B
e e
Mirror
Parity Inverted Original
Figure 10.5 : Wu Experiment
The counts observed in original set up in the direction of opposite to the field are
40% higher than that in the direction of field but this observation is not maintained
in parity inverted set up.
Electrons were emitted preferentially in the opposite direction of the nuclear spin.
205
60
Co 60 Ni* e e
Backward emission is 40% higher .[Wu and coworkers]
Hence in weak interaction neutrinos and electrons are left handed. Yang and Lee
suggested that in beta decay and in general in weak processes, parity is violated so
Lagrangian density and matrix element both must have even and odd couplings.
Parity Violation Puzzle :
P Mode
K 0 12 1
K 13 1
K 0 0 13 1
K decay forced to argue that Parity invariance fails in weak processes [Yang
&Lee]
10.10
10.10 V−A
V−A Theory
Theory of of Fermi Beta Decay
Decay with
with Parity
Parity
Conserving
Conservingand
andNonconserving
NonconservingTerms
Terms
Now we shall discuss the arguments to establish the V−A form of weak
interaction.
Let us write the most general matrix element for the beta decay of neutron.
n p e e
That is consistent with Lorentz invariance and Lepton –Baryon conservation.
M g d pOˆ j n eOˆ j C j Cj 5 e
nucleons j
it is summed over all nucleons inside the nucleus.
nucleons
j Ô j Symbol Meaning
j
j 1 1 S Scalar
j2 V Vector
j 3 T Tensor
206
j4 5 A Axial Vector
j 5 P 5
Pseudo scalar
: It is summed over all type couplings SVTAP and each has left and right
j
handed terms.
1 5 1 5
C j
C
j 5
C j
C
j
2
C j
C
j 2
1 5
: Right handed term (10.63)
2
1 5
: Left handed term (10.64)
2
We use the definitions of matrices
We obtain
O j
ˆ 1 1 O
5 5
ˆ
j for j 1 , 3 , 5 (10.65)
S T P
O j
ˆ 1 1 O
5 5
ˆ
j for j2 , 4 (10.66)
V A
Now we use the experimental fact that all electrons and neutrinos are left handed
1 5
so Ô j terms will vanish.
2
Hence C j C j (Wu-Experiment)
Now Oˆ j 1 5 1 5 Oˆ j for j 1 , 3 , 5
S T P
O j 5 5
ˆ 1 1 Oˆ
j for j2 , 4 (Wu-Experiment)
V A
Therefore
O j j
ˆ C C
j 5
j 1,3 ,5
C j 1 5 O
ˆ
j
j 2 ,4
ˆ
C j 1 5 O j
207
We now apply the result of 152Eu Goldhaber experiment which measures circular
polarization of photons. It results in the assignment of helicity of neutrinos.
.P v
h e 1
P c m 0
e
(Experiment-Goldhaber)
CS
0.001 0.006
CV
CT
0.004 0.001 (10.67)
CA
Next we consider that neutrons in decay are not relativistic and transfer of
momentum of the order of q 1MeV
v2 2
This introduces 2
106 factor in M calculation.
c
v2
It shows that CP is negligible [Exp- c 2 ]
Hence CS ,CT ,CP all are negligible .
Christensen et.al. (1969) measured decay rates of 0 0 transitions in
10
C 10 B
14
O 14 N
and concluded that CV 1 [Experiment –Christensen]
Krohn et.al (1975) measured neutron’s mean life time which yielded
CA
1.258 0.015 [Experiment-Krohn]
CV
Now eC j 1 5 Oˆ j e
eCV 1 5 eCV 1 5
e
e
V ,A
eCV 1 5 5 e
2
5
1
eCV 1 5 1 5 e
1 5 eCV 1 5 e
e
1 5 eCV 1 5
1 5 eCV 1 5
e
208
Hence we justify (V−A) law for beta decay and weak processes in general using
the empirical fact of parity violation.
10.11
10.11Self
SelfLearning
LearningExercise
Exercise
Q.1 Describe Fermi theory of decay and derive transition probability for
decay.
Q.2 Describe - puzzle and Wu experiment of parity violation in decay
of 60Co .
Q.3 Discuss energetics of decay , decay and EC processes.
10.12
10.12Summary
Summary
decay : ZA X Z A1Y e e ; Q
M Z BZ M Z 1 BZ 1
decay :
A
Z
X Z A1Y e e ; Q M Z BZ M Z 1 BZ 1 2me
Electron capture(EC) : ZA X e Z A1Y e ; QEC MZ BZ MZ1 BZ1 b Ze K
general characteristics of weak interaction processes.
(i) universal weak coupling constant
(ii) W ,W and Z o Vector Bosons are Weak Interaction Carriers:
(iii) Range of weak interaction is very short ( 103 fm ):
(iv) SU3 Flavour Symmetry Mixing:
(v) Parity Nonconservation
The probability of transition by Fermi Golden rule
2
2
1 GV M if 2
Ee dEe
2 3 7 c5
F Z ,Ee E0 Ee pe Ee dEe
General Selection rules for beta decay
Fermi I n, n 1 ; f i 1n
n
Gamow Teller I n, n 1 ; f i 1
The allowed or forbidden nature of transitions is often determined from the
measurement of ft 1 2 values.
209
Yang and Lee suggested that in beta decay and in general in weak processes,
parity is violated.
10.13
10.13Glossary
Glossary
decay : , and electron capture
GT Transitions : Gamow Teller Transitions
10.14
10.14Exercise
Exercise
Q.1 Describe Fermi theory of decay and obtain the expression for partial
decay for for channel.
Q.2 Distinguish between Fermi and Gamow Teller transitions by giving one
example for each case.
Q.3 Give salient points of hypothesis of Fermi theory of decay and derive
expression for f t1/ 2 value (comparative half life).
Q.4 Derive transition probability for decay using Fermi theory. Discuss Fermi
Kurie plots.
Q.5 Write short notes on
(i) Basic characteristics of weak interaction (ii) Cabbio angle
(iii) Kobayashi Maskawa Matrix (iv)Vector Bosons W ,W and Z 0
Q.6 Write basic steps of V A Fermi theory explaining the meaning of
S ,V , A,T ,P terms.
References
Referencesand
andSuggested
SuggestedReadings
Readings
1. Nuclei and Particles by Emilio Segre
2. Nuclear Physics by R.R. Roy and B.P. Nigam
3. Introductory Nuclear Physics by Samuel S.M. Wong
4. Elements of Nuclear Physics by W.E. Burcham
5. Theoretical Nuclear Physics by John M. Blatt &Victor F. Weisskopf.
6. Nuclear Physics by S.N. Ghosal
7. Nuclear Models by Walter Greiner & Joachein A. Mahrun
8. Introductory Nuclear Physics by Kenneth S. Krane
210
UNIT-11
Gamma Ray Emission
Structure of the unit
11.0 Objectives
11.1 Introduction
11.2 The Quantized Electromagnetic Field
11.3 Weisskopf Single Particle Estimates for Transition –Probabilities
11.4 Selection Rules and Parity
11.5 Internal Conversion and Pair Production
11.6 Self Learning Exercise
11.7 Summary
11.8 Glossary
11.9 Exercise
References and Suggested Readings
11.0Objectives
11.0 Objectives
The reader learns about electromagnetic transition probabilities and selection rules
for multipoles.
11.1
11.1Introduction
Introduction
Gamma ray is an electromagnetic wave. Gamma decays have theoretical and
practical importance in nuclear physics as gamma rays are source of information
about nuclear energy levels. The concept of quantized electromagnetic field is
introduced. Weisskopf single particle estimates for transition probabilities are
discussed. In this unit we also study internal conversion and nuclear isomerism.
We have used CGS units in this unit.
11.2
11.2The
TheQuantized
QuantizedElectromagnetic
ElectromagneticField
Field
The vector electromagnetic potential A r ,t is taken as the principal dynamic field
211
which is constrained by Coulomb Gauge (Transverse Gauge). The vector field
fulfils the gauge condition
.A 0 (11.1)
and in the absence of charges or currents, the wave equation
1 2 2
2 2 A 0 (11.2)
c t
The electromagnetic fields are given in terms of A r ,t by
1 A
E ,
c t
H A (11.3)
The energy density of the field is
1 2 2
E em
E H (11.4)
8
With a plane waveform for vector electromagnetic potential
Ak r ,t A0 cos k .r t (11.5)
The above equations (11.3) & (11.4) become
Ek kA0 sin k .r t ,
H k k A0 sin k .r t (11.6)
and the energy density of the field will take the form
1 2 2
E em
k A0 (11.7)
8
For a vector field corresponding to one photon of energy in the system volume
V , the amplitude of the electromagnetic vector potential becomes
8 8c 2
A0 (11.8)
k 2V V
Taking ck ,the corresponding complex expression of the dynamic vector
potential which yields the same average energy density is
2c 2 i k .r t * i k .r t
A r ,t a 0e a0 e (11.9)
V
212
where a0 is a complex number with a0 1which determines the phase of the wave
and is the unit vector indicating the polarization .We know that electromagnetic
waves are transverse in nature and there are two independent polarization
directions l ,l 1,2 both fulfilling l .k 0
The classical interaction Hamiltonian density is
1
H j r .A r (11.10)
c
With j r the current density .The transition matrix element between i and f
nuclear states which describes emission of a photon is
3 1
d r f
, ĵ r .A r i ,no (11.11)
c
and for absorption of a photon
3 1
d r f
,no ĵ r .A r i , (11.12)
c
The electromagnetic vector potential operator should thus contains two Hermitian
conjugate parts involving creation and annihilation operators for photon. Hence a0
and a*0 amplitudes in equation (11.9) must be replaced by † and , the creation
and annihilation operators for photons.
The matrix element for emission of a photon of energy ,the total time
dependent phase is
i i
E f Ei t i E f Ei t it
(11.13)
with the unknown phase for creation of a photon in the radiation field .The
conservation of energy implies E f Ei and consequently we have t .
The annihilation operator and creation operator are associated with outgoing plane
waves ( k ) and incoming plane waves k respectively. The mode of the field is
thus specified by wavevector k and polarization index . The electromagnetic
vector potential operator will thus be specified by indices defining mode. The
energy of electromagnetic field is given correctly by number of photons if
2c 2
normalization factor is ensured . The electromagnetic vector potential
V
213
operator summed over all modes k , is
ˆ r ,t 2c 2 ˆ * i k .r t i k .r t
A V k e †k e (11.14)
The choice of and angular momentum projection should go with creation
operator †k .
The total energy of this field integrated over the volume V is given by
ˆ 1
Ĥ k †k (11.15)
k 2
k ,
and the total momentum is
ˆ
p̂ k †k (11.16)
k
k ,
The photon states are treated as eigen states of the momentum operator p̂ . The
interaction with nuclei is best understood if we use angular momentum eigen
states.
Note on :
The photon of energy has an intrinsic angular momentum of 1 with basis
vectors given by spherical unit vectors e , 1,0,1.
The normalized vectors are
1
e1
eˆ ieˆ y
2 x
e0 eˆ z
1
e1
eˆ ieˆ y
2 x
(11.17)
Spherical basis vectors are complex vectors and orthogonal
e*e (11.18)
The Condon-Shortley choice of phases yields the property
e* 1 e (11.18a)
The careful reader will notice that this is analogous to spherical harmonics.
214
Any vector a can be decomposed in spherical basis in the following manner
1
a* e a (11.19)
1
a1 : describes a vector with positive angular momentum of unit 1 about z axis.
The Hamiltonian for the charged particle is written as
1 q 2
H p A (11.20)
2m c
which is sum of free particle Hamiltonian H 0 and the coupling with the external
electromagnetic field giving perturbing Hamiltonian H
H H0 H (11.21)
Comparing (11.20) and (11.21) ,we get
q q2
H
2mc
p.A A.p
2mc 2
A.A
q q2
H
mc
A.p
2mc 2
A.A (11.22)
Using p i and .A 0
( .A is known as transversality condition)
A.p p.A was obtained and used .The quadric term A.A involves two photons at
same time and therefore will be ignored because our interest is in lower order
phenomena. H may be written in terms of a current density ĵ
q
ĵ qv pˆ (11.23)
m
The perturbing Hamiltonian H (neglecting quadratic term ) is
1
H A. j (11.24)
c
1 4
A j
c 1
(11.25)
where
A A,iV and j ( j , ic .
In the region , outside any sources, the electromagnetic vector potential is the
215
solution of the partial differential equation
2 1 2
2 2 A r ,t 0 (11.26)
c t
The 3 vector potential A r ,t
can be expanded in terms of components
characterized by definite wavenumber k as
A r ,t Ak r e it (11.27)
k
where ck . In this relation ,time dependence is separated.
The spatial dependence of A r ,t is given and constrained by
2
k 2 Ak r 0 (11.28)
The solution of this equation can be written as
ˆA r ,t 1 ˆ * i k .r t † i k .r t
e
N
e
k k
(11.29)
k ,
and ei k .r t can be expanded in terms of eigen functions of
* i k .r t
e
angular momentum operators,
 r ,t A r ,t (11.30)
,
A r ,t are vector functions of spherical tensor of ranks , which satisfy the
relations
J 2 A r ,t 1 A r ,t ,
and J z A r ,t A r ,t (11.31)
A r ,t can be expressed in terms of vector spherical harmonics defined by
l
X Y , (11.32)
1
A r ,t appearing in (11.30) and (11.31) can be expanded in terms of electric and
magnetic 2 poles spatially.
E
M
A r C A E ,r D A M ,r
(10.33)
216
Symbols mean as
A E ,r Electric multipole 2 pole type vector potential
A M ,r Magnetic multipole 2 pole type vector potential
A E ,r and A M ,r are solutions of Helmholtz equation
2
k 2 A G ,r 0 (10.34)
where G E,M
The relations between fields and vector potential near the source are given by
1
E E ,r
A E ,r ikA E ,r
c t
H E ,r A E ,r ikA E ,r
1
E M ,r
A M ,r ikA M ,r
c t
H M ,r A M ,r ikA M ,r
(11.35)
The magnetic 2 pole radiations obey equations
2
k 2 E M ,r 0 ,
.E M ,r 0
i
H E ,r
E M ,r
k
r.E 0 (11.36)
Similarly ,the electric 2 pole radiations obey equations
2
k 2 H M ,r 0
.H E ,r 0
i
E M ,r
H E ,r
k
and r .H 0 (11.37)
217
In terms of spherical harmonics ,the electric and magnetic multipole radiations or
transitions can be expressed in the following forms
i
k
A E ,r r j kr Y ,
and
A M ,r r j kr Y ,
(11.38)
where j kr is spherical Bessel function of order and Y , is spherical
harmonics of ranks , .
We can now express the multipole , part of the perturbing Hamiltonian H
[refer to eq.(11.24)] in the form:
i 2 1!!
Ô E 1
ĵ r . r j kr Y ,
ck 1
and Ô M 1
2 1!!
ĵ r . r j kr Y ,
ck 1 (11.39)
where 2 1!! 1 3 5 2 1
The Ô E and Ô M are scalar operators in the nuclear and
electromagnetic fields. So multipole part of current density ĵ r can make a
nonvanishing contribution in the transition for , multipole only. The
spherical Bessel function may be expanded in power series as
2
kr 1 kr
j kr 1 ... (11.40)
2 1!! 2 2 3
The ray involved in nuclear transitions here energies E 10MeV typically. The
corresponding wavenumbers of order
E 10 MeV 1
k fm 1 or less.
c 200 MeV . fm 20
The multipole operators cannot have contributions from the regions outside the
nucleus because they act on nuclear wavefunctions. This leads us to the
r R (nuclear radius) ,but the highest value of R 208 Pb 7 fm. As a result ,
1 1
kr fm 1.7 fm 1. The spherical Bessel function (refer to equation 11.40)
20 3
218
thus converges very fast and we may approximate it by just retaining the first term
alone. This yields
j kr
kr
2 1!!
which means j kr kr . Physically , the observation that wavelength of
2c 2 200 MeV fm
energies E
10MeV is
120 fm.
This is very large in
E 10MeV
comparison to nuclear dimension /radius. This is the reason of calling it long
wavelength limit of radiation.
Applying the Fermi Golden Rule to calculate the transition probability for
multipole 2 radiation from initial nuclear state J i M i to final nuclear state
JfMf .
2 2
W ; J i J f
J i , H J f , Ef
8 1 k 21
2 1!!
2
.
B ; Ji J f (11.41)
where B ; J i J f is the reduced transition probability .The reader should
note that the reduced transition probabilities are dimensional physical quantities.
For electric 2 pole transitions, B E are measured in e2 fm 2 units and for
magnetic 2 pole transitions, B M are measured in 2N fm 22 units. The
transition probability W is the number of decays per unit time. The expressions
for transition probabilities are
21
8 1 1 1
W E c 2 c
E21 MeV B E e2 fm2 (11.42)
2 1!!
2
8 1 1 1 21
E21 MeV B M 2N fm
22
W M c
2M pc 2 1!!2 c
(11.43)
219
Table 11.1
Electromagnetic transition probabilities for the lowest four multipoles.
W E1 1.59 1015 E3B E1 W M 1 1.76 1013 E3B M 1
W E 2 1.23 109 E5B E 2 W M 2 1.35 107 E5B M 2
W E3 5.71102 E7 B E3 W M 3 6.31100 E7 B M 3
W E 4 1.70 104 E9 B E 4 W M 4 1.88 106 E9 B M 4
E MeV ,B E in e2 fm2 and B M in 2N fm
22
11.3 Weisskopf
11.3 Weisskopf Single
Single Particle Estimates
Estimates for
for Transition-
Transition-
Probabilities
Probabilities
We can enumerate the motivation for having reasonable estimates for transition
probabilities between initial and final nuclear states:
1. We can simplify the tedious and lengthy calculations by making a few
reasonable assumptions and approximations.
2. We can make an estimate of sizes of B E and B M that are expected
on the average. W E and W M are dominated by energy dependent
factor k 21 but B E and B M are intimately linked with transition
matrix element.
3. These estimates provide the basis with which observed transition rates can be
compared with theoretical estimates.
E Transitions:
The average of r is
3 3
r r A (11.44)
3
where r0 1.2 fm .
The estimate for reduced transition probabilities B E is taken as
220
1 2 2
Best E e r (11.45)
4
Using eq.(11.44) and (11.45) we obtain Weisskopf Single Particle estimate for
electric 2 pole transition probability is expressed as
2
1 3 2 2 / 3 2
e fm 2
BW E 1.2 A (11.46)
4 3
M Transitions:
The average of r 1 may be taken to be
1
3 1
r
1 3
r A (11.47)
3 0
The factors related to gyromagnetic ratios can be reasonably averaged to
2
2g
2 1 g s l 10 (11.48)
1
The Weisskopf Single Particle estimate for magnetic 2 pole transition probability
is expressed as
2
10 3 2 2 2 2 / 3 2
N fm
2 2
BW M
1.2 A (11.49)
3
The results of (11.46) and (11.49) may be substituted into (11.41),(11.42),(11.43)
to produce the Weisskopf units for transition probability
2 1 2
8 1 1 1 1 3 2 1
W W
E c
2 E MeV
2 1!! c 4 3
2
1.2 A2 / 3 e2 fm 2 (11.50)
2
8 1 1 1 21 21 10 3
2
W W M c E MeV
2M p c 2 1!! 2 c
3
2 2 2 2 / 3 2
fm
2 2
1.2 A (11.51)
N
The explicit values in terms of nucleon number /mass number A and transition
energy E MeV are listed in table 11.2.
221
Table11.2
Weisskopf Single Particle Estimates for E and M transition probabilities
and widths.
Multipole E
M
1 W s 1.02 10
1 14
A2 / 3 E3 W s 3.15 10
1 13
E3
MeV 6.75 108 A2 / 3 E3 MeV 2.07 108 E3
2 W s 7.28 10
1 7
A4 / 3 E5 W s 2.24 10
1 7
A2 / 3 E5
MeV 4.79 1014 A4 / 3 E5 MeV 1.47 1014 A2 / 3 E5
3 W s 3.39 10 A E
1 2 7
W s 1.04 10
1
A4 / 3 E7
MeV 2.23 1020 A2 E7 MeV 6.85 1021 A4 / 3 E7
4 W s 1.07 10
1 5
A8 / 3 E9 W s 3.27 10
1 6
A2 E9
MeV 7.02 1027 A8 / 3 E9 MeV 2.16 1027 A2 E9
W s 2.40 10
1 12
A10 / 3 E11
W s 7.36 10
1 13
A8 / 3 E11
5
MeV 1.58 1033 A10 / 3 E11
MeV 4.84 1034 A8 / 3 E11
In terms of Weisskopf units, the measured reduced rates have been observed to
vary several orders of magnitude in different nuclei and sometimes even for the
transitions within the same nucleus. This enhancement of a transition with respect
to the single particle Weisskopf estimates indicates the collective motion of a
several nucleons in a coherent manner .This will produce nuclear vibrations and
rotations.
11.4
11.4Selection
SelectionRules
Rulesand
andParity
Parity
If for a transition of certain multipolarity , the transition element vanishes then
the transition is called “forbidden”. If , on the otherhand ,for a transition of certain
multipolarity , the transition element does not vanish ,then the transition is called
222
“allowed” .This criterion yields selection rules.
Let us consider the transitions of multipolarities and 1 of E and M
types .The ratios
W E 1
R E W
WW E
WW M 1
and R M W
W
M
can be estimated approximately using (11.50) and (11.51). The ratios
R M ,E also.
1
We obtain k for 1MeV ray to be fm1 and taking r to measure up to 1fm .
200
2
2 1 5
We get R E kr 3 10
200
and R M 3 105 (11.52)
2
The factor is approximated to be (taking c 200MeV fm and
2M P c
M p c 2 940MeV )
2 2 2
200 1 2
10
2M P c 2 940 10
This leads to
2
R M ,E 102 (11.53)
2M pc
Transition between initial J i
i
and final nuclear state J
f
f
is usually
dominated by the lowest order process allowed by angular momentum and parity
selection rules because of the large reduction in probability with increasing
multipolarity order . The angular momentum carried by photon is for
transition of order.
223
The law of conservation of total angular momentum gives an additional
vectorial relation between Ji ,J f and . Here is the angular momentum carried
by the 2 -pole radiation ,and a relation between their z components mi ,m f and .
The transition amplitude vanishes unless
J i J f and mi m f (11.54)
The equation further signifies
Ji J f Ji J f (11.55)
If Ji 0 ,J f 0 then 0 0 transition is absolutely forbidden.
The parity of multipole radiation is specified by the parity of the magnetic field
H E and H M which are 1 and 1 . We have chosen this
because the parity of the perturbing Hamiltonian H (refer to eq.11.24) has the
parity of the H field. The parity of current density j is negative and the parity of
A is opposite to that of H .
Now consider a nuclear transition from initial state i to final state f with i
and f parities. The conservation of parities demand the relation between initial
and final states parities as following
i f 1 for E radiation
1
and i f 1 for M radiation (11.56)
11.5
11.5Internal
InternalConversion
Conversionand
andPair
PairProduction
Production
When an excited nucleus makes a transition from one level to another by emission
of photon (electromagnetic radiation) when it is isolated and deprived of all its
atomic electrons. The presence of orbital electrons makes possible a different
process:
The excited nucleus loses excitation and transfers it to one of the electron of K or L
or M shell. This process is called conversion electrons.
The another competing process of emission of radiation can be compared for a
given transition from an excited state.
224
The ratio of average number of conversion electrons and average number of
photons is called conversion coefficient .
Ne
(11.57)
N
The partial conversion coefficient K , L ,... are ratios for K,L,.. electrons ejection
respectively.
K L M ....
The energy of conversion of electron from K shell is given as
EKCE Ei E f bZh K (11.58)
The conversion electron spectrum is discrete and not continuous such as in
decay where it is continuous and broad peaked.
If energy of nuclear excitation is greater than 2mec 2 , then pair production may
occur .
Ejectedelectron
KShellelectron
e
e e e
e
Ze Ze Ze Ze
Ei Ef Ei Ef
Figure11.1: Pair production in the Figure 11.2 : Internal conversion of
presence of a heavy nucleus Ze an orbital electron due to
electromagnetic interaction with a
nucleus.
Nuclear Isomerism
Some time a nucleus releases energy decaying into lower state with a life time of
the order of 100ms to several years. The nucleus may then decays into a new
nucleus . These states of longer lifetime are called isomer states. This phenomenon
is called nuclear isomerism .The isomer levels are shown in figure 11.3.
225
Nucleus A
a
iA
b iA B
Nucleus B
a B B Nucleus B
b
a
iA B b
Isomeric transition Isomeric transitions
dominant arenot dominant
Figure :11.3
The schematic diagram explaining two types of nuclear isomers through
decay into daughter nuclei B and B of a parent nucleus A.
11.6Self
11.6 SelfLearning
LearningExercise
Exercise
Q.1 Write multipole expansion of electromagnetic field in presence of the
sources of radiation.
Q.2 Write the expression for the Weisskopf single particle estimates of the
transition probability for the multipole radiation of order . Discuss the
result.
11.7
11.7Summary
Summary
For a vector field corresponding to one photon of energy in the system
volume V ,the amplitude of the electromagnetic vector potential is
8 8c 2
A0
k 2V V
The total energy of this field integrated over the volume V is given by
ˆ 1 and the total momentum is p̂ k †
Ĥ k †k ˆ
k 2
k k
k , k ,
A E ,r
A M ,r
and are solutions of Helmholtz equation
2
k 2 A G ,r 0
where G E,M
226
Magnetic 2 pole radiations Electric 2 pole radiations
2
k 2 E M ,r 0 ,
2
k 2 H M ,r 0
.E M ,r 0
.H E ,r 0
i i
H E ,r
E M ,r E M ,r
H E ,r
k k
r.E 0 r .H 0
The expressions for transition probabilities are
21
8 1 1 1
W E c 2 E21 MeV B E e2 fm2
2 1!! c
2
8 1 1 1 21
E21 MeV B M 2N fm
22
W M c
2M pc 2 1!! c
2
The transition amplitude vanishes unless
J i J f and mi m f
If Ji 0 ,J f 0 then 0 0 transition is absolutely forbidden.
The relation between initial and final states parities as following
i f 1 for E radiation and
1
i f 1 for M radiation
The excited nucleus loses excitation and transfers it to one of the electron of
K or L or M shell. This process is called conversion electrons.
11.8
11.8Glossary
Glossary
Coulomb Gauge : The vector field fulfils the gauge condition .A 0
j kr : spherical Bessel function of order
Y , : spherical harmonics of ranks ,
11.9
11.9Exercise
Exercise
Q.1 Define transition probability for emission of a multipole radiation of order
227
, by a nucleus .Discuss briefly spin and parity selection rules for these
transitions .
Q.2 For transitions between low lying states of nuclei (using long wavelength
v
approximation) show that
M p cR c
Q.3 Write short note on
(i) Internal conversion of electrons
(ii) Parity and selection rules for emission of multipole radiations in nuclei.
(iii) 0 0 Transitions in nuclei.
Q.4 When the transition probability is larger than the Weisskopf estimates of the
single particle transition probability for multipole radiation of order ,for a
nucleus what are the possible reasons ?
Q.5 What are the conventional units of reduced transition probabilities
B E ; J i J f and B M ; J i J f ? Show that the difference
of dimensions between these units by analyzing the units dimensionally .
Q.6 Calculate ratios
W E 1
W M 1
W M
RE W , RM W and RME W by
WW E WW M WW E
making approximations .The symbols have their usual meaning.
References
Referencesand
andSuggested
SuggestedReadings
Readings
1. Nuclei and Particles by Emilio Segre
2. Nuclear Physics by R.R. Roy and B.P. Nigam
3. Introductory Nuclear Physics by Samuel S.M. Wong
4. Elements of Nuclear Physics by W.E. Burcham
5. Theoretical Nuclear Physics by John M. Blatt &Victor F. Weisskopf.
6. Nuclear Physics by S.N. Ghosal
7. Nuclear Models by Walter Greiner & Joachein A. Mahrun
8. Introductory Nuclear Physics by Kenneth S. Krane
228
UNIT-12
Sommerfeld Theory of Hydrogen Atom
Structure of the Unit
12.0 Objectives
12.1 Introduction
12.2 Sommerfeld’s elliptic orbits
12.3 Sommerfeld’s Relativistic Correction
12.4 Shortcomings of Bohr- Sommerfeld theory
12.5 Illustrative Examples
12.6 Self Learning Exercise-I
12.7 Interpretation of quantum numbers for hydrogen atom
12.8 Electron probability density
12.9 Orbital angular momentum
12.10 Illustrative Examples
12.11 Self Learning Exercise-II
12.12 Summary
12.13 Glossary
12.14 Answers to Self Learning Exercises
12.15 Exercise
12.16 Answers to Exercise
References and Suggested Readings
12.0
12.0Objectives
Objectives
Bohr was able to calculate the radii as well energies of the stationary orbit around
the nucleus in an atom and those calculated values were found to be in a good
agreement with the experimental values. He also gave the Hydrogen ion spectrum.
For these reasons, his theory was widely accepted throughout the world. But a few
years later, the use of high resolving power spectrometer revealed fine structure of
the hydrogen spectral lines which couldn’t explained by Bohr’s model .To explain
hydrogen fine structure ,Sommerfeld extended Bohr Theory .In this chapter we
will study about Bohr- Sommerfeld theory.
229
12.1
12.1Introduction
Introduction
In 1916,Sommerfeld, in an attempt to explain the fine structure of hydrogen atom,
extended Bohr’s model by considering that the electron could revolve in elliptic
orbits also, apart from Bohr’s circular orbits. He estimated the size and shape of
the possible elliptic orbit and the total energy of an electron revolving in such orbit.
According to Sommerfeld, the stationary orbits in which electrons are revolving
around the nucleus in the atom are not circular but elliptical in shape. It is due to
the influence of the centrally located nucleus. The electron revolves in elliptical
path with nucleus at one of its foci. So there will be a major and a minor axis of the
path. He said that with the broadening of the orbit, the lengths of the two axes
approach to equal value and ultimately become equal i.e. the path become circular.
So we can say that the circular path is just one special case elliptical path.
12.2
12.2Sommerfeld’s
Sommerfeld’sElliptic
EllipticOrbits
Orbits
Let us consider an electron mass (m), and charge (-e) is revolving around nucleus
(charge +Ze) in an elliptic orbit(Fig.1), where and are the semi-major and
semi-minor axes of ellipse respectively.
Figure 1. An electron of mass (m), and charge (-e) is revolving around nucleus
(charge +Ze) in an elliptic orbit.
The r and θ are the polar coordinates of electron at instantaneous position. It
should be periodic functions of time, must be quantized separately,where the p and
j are the radial and angular momentum of the electron respectively.
Then according to Wilson –Sommerfeld quantization rules, we know
230
∮ = ℎ (1)
and ∫ = ℎ (2)
where and are integers, known as radial and azimuthal quantum numbers
respectively.
In second integral, according to classical mechanics, the angular momentum j of
any isolated system is constant. Thus,
∫ = ℎ
or = (3)
This condition of the orbital angular momentum is similar to Bohr model.
To solve the first integral,
= ̇ (4)
and = θ̇, (5)
where ̇ and ̇ are the radial and the angular velocity of electron.
The polar equation of the ellipse
= (6)
where √1 − =
Taking differentiation of r with respect to , we get
− = (6.a)
1 1 sin
− =
1−
Using equation (6)
=−
By squaring the both sides of above equation, we get
=( (7)
)
Now, = ̇ = =
=
̇
231
Using equation (5),we have = (8)
We can write =
:. =
Using equation (7), we get
sin
=
(1 − cos )
Hence the integral in equation (1) becomes
∫ (
= ℎ (9)
)
Solution of this integration is
∫ (
=2 −1 (10)
) √
Using eq.(10) in eq.(9),we get
1
2 −1 = ℎ
√1 −
From eq.(3) put value of
1
ℎ −1 = ℎ
√1 −
or −1=
√
or √1 − =
But we know from property of ellipse
√1 − = ∴ = (11)
where and are integers,
+ = ,
We can write
√1 − = (11.a)
So = (12)
232
This is quantum condition for elliptic orbits.
Here is principal or total quantum number. When n = l, b = a and ε = 0, the orbit
becomes circular. l cannot be zero, since the ellipse would then degenerate into a
straight line passing through the nucleus. Also l cannot be greater than n, since b is
always less than a. Hence for a given value of n, quantum number l can take only n
different values, which means that there can be only n elliptical orbits of different
eccentricities.
Total energy of an electron in an elliptical orbit
Let us now calculate total energy of an electron in elliptic orbit. It will be sum of
the kinetic energy and the potential energy . Then total energy of an electron
will be
= + (13)
The kinetic energy of an electron = ̇ + ̇
using eq.(4) and (5),we get
= +
The potential energy of an electron =−
Putting the values of and in equ.(13), we have
= + − (14)
Using eq.(8)
1 1
= +1 −
2 4
or = + −1 (15)
From eq.(6.a)
1 1 sin (1 − cos )
= =
(1 − ) [ (1 − )]
= [ ( )]
(16)
233
Using eq.(6)
(1 − ) = 1 − cos
cos = 1 − (1 − )
Squaring both sides of equation, we get
(ε cos ) = 1 − (1 − ) (17)
Putting the value of eq.(17) in eq.(16)
1
= − 1 − (1 − )
(1 − )
2 (1 − )
= − 1+ (1 − ) −
(1 − )
r ε r 2r
= − + −1
a (1 − ε ) r (1 − ε ) a (1 − ε )
− 2
= + −1
(1 − ) (1 − )
(1 − ) 2
=− + −1
(1 − ) (1 − )
=− ( )
+ ( )
−1 (18)
Comparing the coefficient of and from equations (15) and (18), we get
=− ( )
(19)
and = ( )
(20)
From equation (19)
=− ( )
(21)
Putting the value of (1 − ) into equation (21) from equation (20),we get
=−
2 4
=− (22)
Again substituting for from equation (20),we get
234
1−
=−
8 2 2
(1 − )
=−
32
Putting the value of (1 − ) and from eq.(3) and (11.a) respectively, we get
4
=−
32 ℎ
=− (23)
This equation shows the energy of an electron in elliptical orbit which is exactly
the same as for the Bohr’s circular orbit. The energy of electron still independent
on the azimuthal quantum number . Thus the introduction of elliptical orbits gives
no new energy levels and hence no new transition. Hence Sommerfeld’s attempt to
explain the fine structure of spectral lines failed.
Size and Shape of Sommerfeld’s Orbits:
From equation (22),we have
=−
8
From equation (23) substituting the value of E, we get
= (24)
= (25)
where = = 0.0529 (Bohr radius)
Again using equation (12)
=
Substituting value of from equation (25), we get
= (26)
We can determine the size and shape of Sommerfeld’s elliptic orbits from equation
(25) and (26).The length of semi-major axis is determined by the principal
quantum number , while the length of the semi-minor axis depends upon the
azimuthal quantum number as well as on .
235
For a given value of , the possible values of are 0,1,2,3..... , when we consider
= 0 ,the ellipse reduces to a straight line and the electron then passes through the
nucleus traversing the orbit. This leads to the collapse of the atom. Therefore the
value of = 0 is forbidden. Thus for given value , quantum number can take
different possible values 1,2,3....... . This means for a given , there are orbits of
different eccentricities which will be occupied by the electron. Let us consider
hydrogen atom (Z=1).
For first orbit = 1, Since + = 1;
≠0 =1
Thus with = and = 0, a=rb and b=rb
Figure 2 : n=1, l=1
This shows circular orbit of radius (Fig.2) which is exactly same as the Bohr’s
consideration. For = 2, Possible values of are 1and 2. we get
(1) = 2, then = 4 , = 4
(2) = 1, then = 4 , = 2
Figure 3.n=1, n=2 orbits.
From above given combination for = 2 ,we have a Bohr’s circular orbit of radius
4 and an elliptic orbit with semi-major axis 4 and semi-minor axis 2 (Fig.03).
But all these orbits have same energy E given by equation (23).
236
For = 3,Possible values of are 1,2 and 3. we get
(1) = 3, then = 9 , = 9
(2) = 2, then = 9 , = 6
(3) = 1, then = 9 , = 3
Thus we find one Bohr’s circular orbit of radius 9 , remaining two are elliptic
orbits with same semi-major axis 9 and different semi-minor axes 6 and 3
which is shown in below figure(04).These all three orbits have same energy.
Figure 4: for = 3, Possible values of are 1,2 and 3.
We can see that for each value of the principal quantum number n, there will be n
different allowed orbits. One of these will be circular, which is explained by the
original Bohr theory. Other will be elliptic, all having the same semi-major axis,
but different semi-minor axes.
The electron is moving in different possible orbits for a given n, but the energy of
electron remains same in all orbits associated to n. Thus we conclude that
Sommerfeld’s introduction of elliptic orbits do not include new energy levels,
hence it cannot explain the fine structure. The orbits associated to same energy
known as degenerate. To represent the different orbits in another notation
corresponding to azimuthal quantum number = 1,2,3,4,etc.. It is described by the
letters s,p,d,f etc. respectively. In this notation, the orbit determined by = 3 and
= 1 is represented by 3s. Similarly 4f will represent the orbit = 4 and = 4.
12.3
12.3Sommerfeld’s
Sommerfeld’sRelativistic
RelativisticCorrection
Correction
An electron has the ratio / ≅ 10 or less in innermost orbit of hydrogen atom.
Due to this, relativistic correction will arise. In elliptic orbit, the velocity of an
237
electron varies point to point in orbit. It is a maximum at nearest the nucleus and a
minimum farther away from the nucleus. According to the theory of relativity, we
know that the variation of velocity means variation of mass of the electron.
Taking this effect into account, Sommerfeld calculated the total energy of an
electron in an orbit which is characterized by the quantum numbers n and l as
∝ 1 3
=− 1+ −
8 ℎ 4
where ∝= = is “fine -structure constant”. It is dimensionless quantity and
equal to the ratio of the velocity of electron in the first Bohr orbit of hydrogen to
the velocity of light c in vacuum.
The above expression may also be written as
ℎ ∝ 1 3
=− 1+ −
4
where = =1.097 × 10 is Rydberg constant for an infinitely heavy
nucleus.
The term values of the hydrogen –like atom are
∝ 1 3
=− = 1+ −
ℎ 4
2 4 2
∞ ∞ ∝ 1 3
or = 2
+ 3
−
4
The first term is similar to Bohr derivation for circular orbits. The second term is
the relativisitic correction ∆ , so we can write
R Z ∝ 1 3
∆T = −
n l 4n
Because ∝ = 5.84
4
5.84 1 3 −1
So ∆ = 3
− (27)
4
Finally we can calculate the relativistic shift in the energy levels of various l values
for each Bohr energy level n with the help of the last expression.
12.4
12.4Shortcomings
ShortcomingsofofBohr-
Bohr-Sommerfeld
SommerfeldTheory
Theory
There are given some shortcomings of Bohr-Sommerfeld theory as following-
238
(1) Bohr’s theory able to calculate the energies of the allowed states of an atom
and the frequency of radiation emitted or absorbed in transitions between
allowed states. But it is unable to calculate the rate at which such transitions
take place and intensity of the spectral lines.
(2) The theory fails for atoms which have more than one electron ,for example
neutral helium atom which has only two electrons. It is applicable only to one-
electron atoms like hydrogen, hydrogen isotopes, singly-ionized helium etc.
(3) Even it was unable to explain the fine structure of spectral lines in the simplest
hydrogen atom.
(4) There were not given proper reason for the introduction of quantum numbers.
The quantum numbers were introduced by Bohr as a postulate.
(5) Both the theories could not explain the distribution and arrangement of
electrons in atoms.
(6) Both the theories could not explain anomalous Zeeman effect and Stark effect.
12.5
12.5Illustrative
IllustrativeExamples
Examples
Example1: Calculate the energy shift from Bohr level of an electron in hydrogen
atom in state of n=1 quantum number using Sommerfeld’s relativistic correction.
Sol. Given principal quantum number n=1, and for hydrogen atom Z=1
Azimuthal quantum number for n=1 will be l=1
Energy shift from Bohr level
∝
∆T = − ,
∴ ∝ = 5.84
Then, putting the given values, we get
.
or ∆T = −
.
or ∆T =
Shift from Bohr level
∆T = 1.46 cm
Example 2: Calculate the ionization energy of hydrogen atom.(h=6.63 x 10-34 J.s,
e = 1.6 x 10-19 C, m = 9.1 x 10-31 kg , and = 8.85 x 10-12 C2/N-m2 )
239
Sol. In case of hydrogen atom (Z=1) ionization energy means binding energy the
electron to the nucleus, which is equal to the energy of the lowest state
corresponding to n=1.
=−
8 ℎ
Using above equation for ionization potential (n=1,Z=1)
=−
8 ℎ
. ( . )
=−
( . ) ( . )
=−2.17 10 =−13.6 ∴1 = 1.60 10
12.6
12.6Self
SelfLearning
LearningExercise
Exercise-I-I
Q.1 What will be shape of orbit corresponding to principal quantum number n=2 ?
Q.2 Why did Sommerfeld introduce relativistic correction?
12.7 Interpretation of Quantum Numbers for Hydrogen Atoms
12.7Interpretation Atom
We consider a simplest bound system, one-electron atom like hydrogen atom that
occurs in nature. It have a positively charged nucleus and negatively charged
electron(-e), moving under their coulomb attraction and bound together by the
attraction. The state of the electron around the nucleus in terms of its location
relative to the nucleus and the energy associated with it is described by a set of
quantum numbers. Each electron is characterized by four quantum numbers called
the principal (total) quantum number, the azimuthal (orbital) quantum number, the
magnetic orbital quantum number and the magnetic spin quantum numbers. Now
we want to describe in term of size, shape, orientation of the orbit in space and spin
around the nucleus.
(1) The total and principal quantum number(n)
This is identical with the one used in Bohr-Sommerfeld’s theory. It can take values
1, 2, 3, 4, ..., ∞. This denotes the major axis of the ellipse with which the energy of
the electron is associated and hence pertains to the main energy level or shell.
These energy levels having values of n = 1, 2, 3, 4, etc. These values represented
by symbols of shells K, L, M, N, etc.
240
The energy (E) of different levels is inversely proportional to . That is
1
∝
(2)The orbital quantum number (l) –
This quantum number is an integer and for a given value of n, it can take any of the
values 0, 1, 2, 3,4, ..., (n – 1). It divides the main shell into n slightly different
energy levels of sub shells so that the number of sub shells in main shell is
represented by its principal quantum numbers. It means the shell with principal
quantum number n=1 or K-shell has only one sub shell represented as s-sub shell
(l=0).
This quantum number is called the angular momentum quantum number,which
represents mechanical angular momentum of the electron. The orbital angular
momentum L is written as
= , where l=0, 1, 2, 3.....etc.
According to quantum mechanics, the value of orbital angular momentum L is not
equal to but given by
ℎ
= ( + 1)
2
The L-shell will have two sub-shells having values l=0 and l=1. They are
represented as s and p sub-shells. Thus we can find different sub-shells associated
to different shells.
(3)Magnetic orbital quantum number ( )-
An electron revolves around the nucleus possesses angular momentum interacts
with an external magnetic field B. The magnetic quantum number represents
the direction of L by determining the component of L in the field direction. This is
known as space quantization.
ℎ
=
2
where = 0, ±1, ±2, … . ±
The possible values of for given value of ranges from + to – . The number
of possible orientations of the angular momentum vector L in magnetic field will
be 2 + 1.
241
For =0, = 0 (only single value)
= 1, = , 0, −
Similarly we can find out different values associated to different .
Figure 5:-Space quantization of orbital angular momentum.
The magnetic spin quantum number( ):-
In 1925 ,two Dutch graduate students, Samuel Goudsmit and George Uhlenbeck,
proposed that every electron have an intrinsic angular momentum called spin,
whose magnitude is half (1/2).It is same for all electrons and associated with this
angular momentum is magnetic moment.
The quantum number s describes the spin angular momentum of the electron. It
follows both Dirac’s theory and from spectral data. The angular momentum S due
to electron spin is given in terms of the spin quantum number s by
ℎ √3 ℎ
⃗= (s + 1) =
2 2 2
The space quantization of electron spin is described by the spin magnetic quantum
number ms. The spin angular momentum vector can have the 2s+1=2 orientations
specified by ms= +1/2 (spin up) and ms= -1/2 (spin down).
Z-component of spin angular momentum
ℎ 1 ℎ
= =±
2 22
242
12.8
12.8Electron
ElectronProbability
ProbabilityDensity
Density
The electron in a hydrogen atom is described by the Schrödinger equation. The
time independent Schrödinger equation in spherical polar coordinates (r,θ,Φ) can
be solved by separation of variable in the form
(r,, ) = R( )() ( )
Quantum mechanically, we cannot consider an electron as moving around the
nucleus in definite orbits. It is probabilistic phenomena. In three dimensions,
probability density (r,, ) gives the probability per unit volume for the
electron to be found in a small volume element at the coordinate (r,θ,Φ).
(r,, ) = | | || ||
∗
where | | = , etc.
The wave function (r,, ) is symmetrical about the z-axis. So | | depends
only | | || . Firstly we will discuss the dependence of | | on | | . For
this we define the radial probability density ( ), this is defined so that
( ) gives the probability that regardless the direction, electron will be found to
the lie between two spheres whose radii are and + , the volume between
these spheres is 4 . So we can write
P(r)dr = ( ) = ( )4 (28)
The graph of ( ) against / , where is Bohr radius ,is given below for values
of and (state 1s, 2s and 3s for the hydrogen atom ( z=1 ) are shown in Fig.6.
Figure: 6 Graph between P(r)and /
243
We can see from fig.6 the electron is most likely to be found at the locations of
Bohr orbits. Now we will consider the dependence of | | on || (directional)
which is shown Fig.7 and Fig.8. The form of || in terms of polar diagram in
which the origin is at = 0 and the z- axis is taken along the direction from which
the angle θ is measured.
Fig.7 Polar diagram for s-state l = 0, ml = 0
Fig. 8. Polar diagrams for p-state (a) ml = 0 (b) ml = ±1 (c) ml = 0 rotated around
z–axis, (d) ml = ±1 rotated around z–axis.
244
From above figures we can say || is constant for an s-state (l=0) and for other
states it varies with θ and takes largest value in definite direction.
12.9
12.9Orbital
OrbitalAngular
AngularMomentum
Momentum
An electron revolves around nucleus in atom which has an orbital angular
momentum ⃗ which have direction along the orbital axis. The angular momentum
⃗ of a particle bound to and moving around a coordinate origin is defined by the
equation
⃗= ⃗x ⃗ ,
where ⃗ and ⃗ are a position vector with respect to origin and linear momentum
vector respectively. The rectangular components of ⃗ are
Using cross product,
= −
= −
= −
where x,y,z are the components of ⃗, and , , are the components of ⃗.
Using equivalent differential operator for momentum components
ℎ ℎ ℎ
=− , =− , =−
2 2 2
Now we get rectangular component of angular momentum in quantum mechanical
operators, which are
ℎ
=− −
2
ℎ
=− −
2
and
ℎ
=− −
2
In spherical polar coordinates these operators become
= sin + cot cos (29)
= − cos φ + cot sin (30)
245
and =− (31)
The square of the magnitude of the angular momentum vector ⃗ is
= + +
The corresponding operator is
= + +
Put the squares of , , from equation (29),(30),(31) we get
ℎ
=− sin + cot cos + sin + cot cos sin
4
+ cos + cot sin
− cos cot sin + cot sin − cos +
By more solving, we get final solution
=− + + cot
ℎ cos θ 1
=− + +
4 sin θ sin
or =− sin + (32)
It is operator of the square of the angular momentum.
By applying the operator to the one –electron atom wave function
(r,, ) = R( )() ( )
This gives =−
or =− R (33)
The function ( ) for the atom is given by
=A
By differentiating w.r.t , we get
=A =
Put this value in equation v, we get
246
ℎ
=− R
2
ℎ
=
2
Given above equation shows the wave functions of the one-electron atom are the
eigenfunction of having eigenvalues given by
= (34)
where = 0, ±1, ±2, … . ±
12.10
12.10Illustrative
IllustrativeExamples
Examples
Example 3: Calculate the two possible orientations of spin vector S with respect to
a magnetic field.
Sol. The magnitude of spin angular momentum S,
⃗= (s + 1) , s=1/2
and z-component
SZ=mS , mS=±1/2
The angle between S and the z- axis is determined by the quantum numbers mS and
S,
cos = = = , (∴s=1/2)
√ ( ) √
For mS=+1/2,we get
cos =+ = 0.577 ∴ = cos (0.577) = 54. 7
√
For mS = - 1/2,we get
cos =− = −0.577 ∴ = cos (−0.577) = 125. 3
√
Example 4: Find the possible values of the components of angular momentum
along a specified direction for an electron orbit with quantum number l=1.
Sol. For the given electron l=1 (p-electron) and s = 1/2
The two possible values of j are
j=l ± s =1±1/2=3/2 and ½
For j=3/2, the possible values are
3 1 3 1
= , ,− ,−
2 2 2 2
247
For j=1/2, the possible values are
1 1
= ,−
2 2
Z – Component of total angular momentum will be
= ,
So the possible values for z-component of total angular momentum
3 ℎ 1 ℎ
± ,±
2 2 2 2
Example 5: How many revolutions does an electron in n=3 state of a hydrogen
atom make before dropping to the n=1 state? The average life time of an excited
state is 10-8 second. ( =1.097 × 10 )
Sol. For hydrogen atom Z=1
The number of revolutions per second of the electron in the orbit is
= /2
For finding the value of from Bohr postulates for condition of mechanical
stability of electron is
1
=
4
and quantum condition is
= (n=1,2,3.......)
We find from above equations
= and =
Thus = = =
For the n = 3 state, the frequency of revolution is
2
=
(1.097 × 10 )(3.0 × 10
= = 3.66 × 10
9
Hence the number of revolutions of the electron in its life-time of 10 second is
=(3.66 × 10 ) ×10 = 3.66 × 10
248
12.11
12.11Self
SelfLearning
LearningExercise-
Exercise-IIII
Q.1 What is the meaning of degeneracy of the elliptic orbits in Sommerfeld’s
theory of elliptic orbits?
Q.2 Calculate the possible orientations of the total orbital angular momentum
vector ⃗ corresponding to = 1 with respect to a magnetic field along the
z-axis.
Q.3 Show that the ionization potential of Li++ is nine times the value for hydrogen
atom.
12.12
12.12Summary
Summary
The unit starts with Sommerfeld’s elliptic orbit. Find the derivation for energy,
shape and size for different elliptical orbits. Sommerfeld’s model can’t explain fine
structure of spectral lines. We introduce relativistic correction for single electron
atoms.
Further, quantum numbers and electron probability density are introduced for
hydrogen atom .We try to draw polar diagrams for different energy states. In last,
we defined orbital angular momentum. There involved many solved and unsolved
problems time to time after derivation.
12.13
12.13Glossary
Glossary
Degenerate–Two or more quantum states that share or relate the same quantum
numbers.
Stationary -Remaining in the same condition or state
12.14
12.14Answers
AnswerstotoSelf
SelfLearning
LearningExercises
Exercises
Answers to Self Learning Exercise-I
Ans.1: There will be to two possible orbits
(i) Circular (with radius 2 )
(ii) Elliptical (with semi-major axis = 4 and semi-minor axis =2 )
Ans.2: To explain fine structure of hydrogen spectral lines.
249
Answers to Self Learning Exercise-II
Ans.1: Orbits have common value of energy known as degenerate orbit and such
property of orbits known as degeneracy.
Ans.2: cos = 0.7071, 0, −0.7071 , = 45 , 90 , 135
Ans.3: Using = − ℎ
12.15Exercise
12.16 Exercise
Q.1 Describe Bohr’s atom model. Assuming that the nucleus is infinitely heavy
and the electron has mass m and charge e, find out the energy of the electrons
moving in the nth orbit. Calculate the ionization potential of hydrogen atom.
Q.2 Calculate the time taken by the electron to traverse the first Bohr’s orbit in
hydrogen spectrum.
Q.3 What are the salient features of Bohr-Sommerfeld atom model ?
Q.4 How many revolutions does an electron in the n = 2 state of a hydrogen atom
make before dropping to the n = 1 state? (The average life time of an excited
state is about 10–8 s).
Q.5 Calculate the possible orientations of the total angular momentum vector ⃗
corresponding to j=5/2 with respect to a magnetic field along the z-axis.
12.17
12.16Answers
AnswerstotoExercise
Exercise
Ans.1: See in section 12.2
Ans.2: 15.26 x10-5 sec.
Ans.3: See in section 12.3 & 12.4
Ans.4: 8.2 x106
Ans.5: 32.220, 59.530, 80.270, 99.720, 120.460,147.770
Referencesand
References andSuggested
SuggestedReadings
Readings
1. Raj Kumar, Atomic and Molecular Spectra: LASER, Fifth edition (2008),
Kedar Nath Ram Nath.
2. Arthur Beiser, Concept of Modern Physics, Sixth edition (2006), Tata
McGraw-Hill .
3. R. Resnick, D. Halliday, K. S Krane,Physics (Volume - I) 5th Edition
(English) Wiley India Pvt. Ltd. 2002.
250
UNIT-13
Vector Atom Model
Structure of the Unit
13.0 Objectives
13.1 Introduction: Vector Atom Model
13.2 Spinning Electrons
13.2.1 Intrinsic Magnetic Moment
13.3 Space Quantization
13.3.1 Orientation of Orbit
13.4 Quantum Number's and Their Physical Interpretation
13.5 Magnetic Moment of an Electron in an Atom and Lande's g factor
13.6 Larmor Precession (Larmor's Theorem)
13.7 Spin-Orbit Coupling: Vector Atom Model
13.8 Quantum Numbers for Multielectron Atom
13.9 Spectral Terms and Their Notations
13.10 Description of Ground State
13.11 Stern-Gerlach Experiment and Electron Spin
13.12 Illustrative Examples
13.13 Self Learning Exercise
13.14 Summary
13.15 Glossary
13.16 Answers to Self Learning Exercise
13.17 Exercise
13.18 Answers to Exercise
References and Suggested Readings
251
13.0
13.0Objectives
Objectives
This chapter is focused on the development of Vector Atom model, which was
conceptualized with two features, namely, the quantization of space (orientations
of orbits) and electron spin. The idea of quantization of orientations was introduced
by the concept of projection of each quantized orbit on the field direction. This laid
down the introduction of additional quantum numbers, namely magnetic orbital
( ml ) and spin quantum number ( mS ). With complete nomenclature of quantum
numbers of single electron system, say Hydrogen atom, this model neatly explains
the periodic table as well as describe the magnetic properties of electron (atom)
and the total angular momentum results from L-S coupling. Stern – Gerlach
experiment provides the direct experimental evidences for the existence of spin of
electron and discrete orientations of orbits, when an atom is placed in a strong non
– uniform magnetic field.
13.1
13.1Introduction
Introduction: :Vector
VectorAtom
AtomModel
Model
The vector-atom model is an extension of Rutherford-Bohr-Sommerfeld atom
model. Rutherford-Bohr-Sommerfeld atom model successfully explains single
valence atom, i.e. Hydrogen atom but incapable of resolving the spectroscopic
issues of atoms contains more valence electrons. Thus, to overcome the limitation
of Bohr-Sommerfeld model as well as to explain new experimental phenomena,
like anomalous Zeeman’s effect, Paschen's–Back effect, Stark effect. Further, the
theory proposed by Bohr and Sommerfeld are two dimensional while an atom is a
three dimensional entity. Therefore, to incorporate the three-dimensional concept
and to explain the complexity of the spectral distributions, extension of Bohr-
Sommerfeld model was given by Uhlenbeck and Goudsmit, known as Vector-
Atom model. The vector atom model basically deals with the total angular
momentum of an atom which is results of the combination of orbital and spin
angular momenta. The main two features of vector atom models are, namely,
spinning electrons and space Quantization of electron orbits.
13.2
13.2Spinning
SpinningofofElectrons
Electrons
Since the Bohr-Sommerfeld model couldn't explain completely the spectral
behavior of Hydrogen atom and thus it became necessary to address some other
properties of moving electron. To describe the multiple character of spectral lines,
252
i.e. multiplets (for example double of sodium, triplet of magnesium and mercury)
and also to account the behavior of spectral lines under the effect of magnetic field,
Uhlenbeck and Goudsmit proposed the hypothesis of spinning electrons in order to
explain some of spectral phenomena such as Zeeman effect, fine structure etc.
According to its, electron revolves about its own axis while revolving in its orbit
around the nucleus. Thus moving electron has two kinds of motion, orbital motion
and spin motion.
As we know that circular motion of a mechanical body leads to mechanical
angular momentum, similarly a charge body, i.e. electron produces a circular
current which also rotates with body. This circular current then gives rise to a
magnetic moment. Therefore, concept of electron spin introduces two angular
momentum and two magnetic moments: one from is due to orbital motion while
other is due to spin motion. The total angular momentum of the electron is the sum
of orbital and spin angular momentum. Similarly, the total magnetic moment is the
sum of orbital and spins magnetic moment.
The spinning motion of electron is quantized in both magnitude and direction. The
intrinsic spin angular momentum is given by
ps s (1)
The intrinsic spin angular momentum is as shown in Fig. (13.1) spin angular
momentum can take only two orientations in the presence of magnetic field.
Fig.: 13.1
The projection of ps is given by
ps z ms (2)
253
with analogy, the orbital angular momentum vector and spin angular momentum
1
vector can have two values (2s+1). For example, if s , ms can have only two
2
1 1
values, namely , or , i.e. spin-up (parallel) and spin-down (anti parallel)
2 2
directions correspondingly and thus ps can take only two orientations.
13.2.1 Intrinsic Magnetic Momentum
Due to the spinning of electron, a circular current is produced which generates a
magnetic field. This field is the same as the produced by a bar magnet and
characterized by magnetic moment µs is given by
e
µs 2 . ps (3)
2m
13.3
13.3 Space
SpaceQuantization
Quantization
In Bohr's model, electron has only one quantum number, namely, principal
quantum number n to describe the motion of electron motion. Thus electron has
only one degree of freedom in Bohr's model. Later on, according to Sommerfeld,
electron revolves in elliptical orbits which are two dimensional and hence electron
has two degree of freedom. Therefore, two quantum numbers namely, principal
quantum number n and the azimuthal quantum number k. But in general, an atom
is a three-dimensional body and therefore, possesses three degree of freedom.
Since, classically, electron orbit may orient in all possible directions in space, i.e.
may take different orientations in the atom, as shown in Fig. (13.2).
Fig.: 13.2
Thus, third quantum number quantizes the orientation of elliptical orbit in three-
254
dimensional space does not change original Sommerfeld orbits, but according to
rule of space quantization, out of infinite possible orientations only certain discrete
orientations are allowed. Therefore, the orientation of an orbit is needed to fixed
up.
13.3.1 Orientations of the Orbit
The preferred direction or orientation of an orbit
can be find out with the help of orbital angular
momentum vector pl which is directed along the
axis of rotation of electron and perpendicular to the
plane of orbit (Fig. 13.3).
The rotating electron about the nucleus forms a
current loop has magnetic moment µ IA , where
I is the current in loop and A is the area vector.
The energy of charged loop is given by µB cos .
Since an orbiting electron possesses angular Fig. :13.3
momentum ( pl ) which interacts with external magnetic field. Therefore according
to quantum theory vector pl can have certain discrete directions relative to external
magnetic field direction, known as space quantization. The space quantization of
an orbit is specified by projection of its orbital angular momentum onto direction
of external magnetic field (along z-direction).
The orbital angular momentum is given by
lh
pl l (4)
2
According to space quantization, pl can have only those orientation for which its
component in the field direction B will take integral values of . From Fig. (13.4),
pl cos is given by
pl pl cos ml
z
(5)
where ml is known as orbital magnetic quantum number and is the angle
between pl and field direction since ml has to be an integer and cos cannot
exceed unity, thus the permitted values of ml are from l to l , i.e. take
following values:
l ,( l 2),(l 2)......,1, 0, 1, 2,......(l 2), l
255
This implies that for each value of l, there will be ( 2l 1) values that ml can have
and pl can have ( 2l 1) possible directions.
Fig.: 13.4: Space quantization of pl for l = 2)
When an atom is subjected to magnetic field, the energy of the electron in
its orbit varies for all relative orientation of pl with respect to field direction.
Now the electron is visualized as three dimensional motion quantized by three
quantum number n, l and ml .
As both the orbital angular momentum pl and intrinsic spin angular
momentum ps that determine the state by quantized vectors and added up as per
the rules of vectors, the atom model is known as Vector Atom model.
Thus, the introduction of quantization of space and quantization of spin of electron
further lead to same new quantum number which we will discuss in next.
13.4
13.4Quantum
QuantumNumber's
Number'sand
andTheir
TheirPhysical
PhysicalInterpretation
Interpretation
In Bohr's Sommerfeld model, two quantum numbers, namely, principal and
azimuthal quantum numbers are defined, which are not enough to describe the
motion of an electron in its orbit. But in vector atom model, each component is
assigned as quantum number whose numerical value may be thought of as the
length of vector and therefore following quantum numbers are used to describe the
motion of an electron completely.
256
(i) Principal Quantum Number (n):– Classically, the principal quantum number
‘n’ represents ordinal number of particular orbit occupied by electron are defined
as K, L, M, N orbit for n = 1, 2, 3, 4 respectively. But in quantum mechanics, no
definiteness is allowed.
The quantum number ‘n’ can take on the integral values 1, 2, 3, 4 ….
1
and governs the total energy En 2 and major axis of elliptical orbit, even it
n
gives the large mean distance of the electron from the nucleus. Thus, the K, L, M,
N …. not only represents the mean distance but also a group of electrons at the
means distance from the orbit.
(ii) An Orbital Quantum Number (l):– The orbital quantum number l can take
on values 0, 1, 2, 3, ……. (n – 1) for each n and governs the orbital angular
momentum ( pl ). It is to be noted that l can have value zero but it is not allowed for
k (azimulthal quantum number), because of the relation l k 1 .
Angular momentum according to wave mechanics is given by
pl l (l 1) (6)
Orbital have the same value of l defines the natural series 0, 1, 2, 3, ….. are
labeled as (s) sharp, (p) principal, (d) diffuse, (f) fundamental …… given to the
lines in the hydrogen spectra.
(iii) Spin Quantum Number (s):– As we have discussed that the quantization of
spin of electron was needed to explain fine structure of spectral line spin of
electron can take ½ only and relates to the intrinsic, property known as spin
angular momentum as
ps s( s 1) (7)
For single electron system ps 0.866
(iv) Total Angular Momentum Quantum Number (j):– It is also known as inner
quantum number. This denotes the total angular momentum of the electron which
arises due to orbital motion and spinning of electron.
For a single electron system, vector l , i.e. pl and s , i.e. ps couple vectorially in a
weak field to given vector j , i.e. j l s and the total angular momentum of the
electron is p j i.e. p j pl ps . The quantized total angular momentum is given by
p j j ( j 1) (8)
257
where j is positive and always ½ integral for a single electron. Each l level
1 1
degenerates into two j levels, namely l and l – .
2 2
When an atom is subjected to a magnetic field, three more quantum numbers are
associated with electron due to space quantization.
Fig. 13.5
(v) Magnetic Orbital Quantum Number (ml):– m l is the numerical value of the
projection of orbital quantum no. (vector l) in the magnetic field direction, i.e. l
precesses about the magnetic field direction and forms a cone about axis. Due to
the rule of space quantization, projection of l must be quantized in the field
direction then l can have orientation in certain directions and m l may also be an
integer, is given by
m l l cos (9)
Possible values of m l are m l l , (l 1), (l 2).........0,...... 1,...... 2....(l 1)....... l
i.e. ( 2l 1) possible orientations of l .
Fig. 13.6
258
The negative values of ml represent that component of angular momentum
is oriented opposite to the direction of magnetic field. Fig. (13.6) shows the
orientations of l and possible values of ml for l 2 .
(vi) Magnetic Spin Quantum Number (ms):– Similar the orbital angular
momentum, ms is the numerical value of the projection of the spin vector ‘s’ on the
field direction and spin vectors can have only (2l +1) values from –s to +s at unit
interval.
(vii) Total Magnetic Quantum Number (mj):– It is the numerical value of the
projection of total angular momentum in the field direction. Since, j can have only
½ integral values m j also assumes half integral values. The permitted orientation of
j are ( 2 j 1) and hence possible values of m j are j ,( j 1) …….. ( j 1) , i.e.,
( 2 j 1) excluding zero.
13.5
13.5 Magnetic
Magnetic Moment
Moment ofof an
an Electron in an
an Atom
Atom and
and
Lande'sLande's
g- Factor
g- Factor
Electron magnetic moment, i.e., electron magnetic dipole moment is the magnetic
moment of an electron produced by intrinsic properties of spin and electric charge.
In an atom, it is known that an electron revolves around the nucleus with certain
angular velocity in a orbit of radius r. This revolution of electron produces the
angular momentum about the centre of the path, is given by
Fig.: 13.7
pl m r 2 (v r ) (10)
which is quantized along the perpendicular direction to the plane of orbit.
From, classical electrodynamics, we know that when a charged body rotates, it
produces magnetic field due to current. This creates magnetic dipoles of equal
magnitude but opposite polarity, which gives rise to the orbital magnetic moment.
Thus, an electron would gives rise to a current in a complete revolution of time
period T is
259
Q e
i (11)
T T
As we also know that the field due orbital circuital current does not depend upon
the shape x and having orbital magnetic moment
µl iA (12)
where A r 2 (Area of orbit)
e e
µl r 2 r 2 (T 2 / )
T 2
e
m r 2
2m
e
µl pl (13)
2m
–ve sign indicates that µe and pl are oppositely oriented. The numerical value of
|µ | e
the ratio of µe and pe , i.e. l gl is known as gyromagnetic ratio.
| pl | 2m
Fig. 13.8
From the quantization of angular momentum ( pl l ) , the orbital magnetic
le
moment µl Joule/Tesla (14)
2m
For the case of ground state of hydrogen atom (n =1), this orbital magnetic moment
is called Bohr-Magneton, given by
e 1.6 1019 1.05 1034
µB J/T
2m 2 9.110 31
9.27 10 24 J/T (15)
Thus, equation (14) is written more correctly as
µl gl µB l (16)
260
Similarly, further, electron possesses an intrinsic spin angular momentum, hence, it
will also have a spin magnetic moment, following the equation (16), spin magnetic
moment can be written as
µs g s µB s (17)
Since spin of electron also leads to a mechanical momentum ( ps ) , thus the ratio of
spin magnetic moment to spin mechanical momentum is
| µs | e
(18)
| ps | m
Since the spin frequency is twice as large as orbital frequency, thus we may write
gs 2
here g s is called "spin-g factor", which gives the numerical measure of magnetic
moment in units of Bohr magneton.
Quantum mechanically, we have
e
µl gl l (19)
2m
e
µs g s s (20)
2m
The total magnetic moment of the atom is the vector sum of orbital and spin
magnetic moment
e
µj g j (21)
2m
This g is called Lande's g- factor.
The potential energy of atomic magnet associated with orbital magnetic moment is
given by
Vm B . B . B cos (22)
where is the angle that the angular momentum makes with the field direction, is
given by (according to the rule of space quantization).
l cos ml (23)
el
and also from equation (14)
2m
e
then Vm B ml (24)
2m
261
13.6
13.6 Larmor
LarmorPrecession
Precession(Larmor's
(Larmor'sTheorem)
Theorem)
In physics, Larmor precession is the precession of the magnetic moment of any
object with magnetic moment in an external magnetic field. The concept of
precession is illustrated below for the earth well as for a spinning top. On both
cases the external force is just gravity.
Fig. 13.09
When a magnetic moment is placed in a magnetic field, it is aligned with
the field. Classically, a magnetic moment can be realized as a current in a loop and
the influence for being aligned by the external magnetic field can be treated as
torque. When a magnetic moment directed at some finite angle with respect to
magnetic field direction, the field will exert torque ( µ B ) on the magnetic
moment, which causes the precession about the magnetic field. Since the magnetic
moment is associated with angular momentum j precesses about an axis parallel
to the magnetic field.
The phenomena of precession can be described in term of (a) angle between
symmetry axis and angular momentum vector, denoted by , and (b) angular
d
velocity p , where the angular displacement in the time internal t is
dt
t obviously.
From the Fig. (13.10), it can be easily written that
j J sin ( p t ) (25)
For an infinitesimally small and J , we may write
dJ
p J sin (26)
dt
262
Fig. 13.10
But the angular momentum cannot change if there is no torque, infact, rate of
change of angular momentum is equal to torque, given by
µ B µBsin (27)
Thus, one may have
µB sin p J sin
µB
p
J
µ e
where g
J 2m
e
p g B (28)
2m
which states that angular velocity of the precession is proportional to the
magnitude of the external field and the proportionality constant . Thus the
ge
2m
frequency of the precession i.e. is given by
p eB
fp g (29)
2 4 m
Since according to the classical theory, in an atom, the electron orbit and
spin should precess in a magnetic field which holds good in quantum mechanical
treatment also but the meaning of precession in quantum mechanics is usually
referred as Larmor' precession and frequencies above are often defined as Larmor'
frequencies, where the constant
ge
is usually written as , known as
2m
263
gyromagnetic (magnetogyric) ratio. Thus,
p B (30)
For a single electron system it is quite simple to understand the behavior of
system. But it becomes more complicated when many electrons are involved,
which further become more complicated when external magnetic field is
introduced. To resolve the issue, Larmor has proved a theorem that basically state
that "motion of the system is the same as it would be in the absence of the field
except that a uniform rotation around the axis of magnetic field."
More specifically, the added rotation will have an angular frequency in an external
magnetic field, equal to
e
L .B (31)
2m
which is the same formula, as we have observed for angular velocity of the
precession when g 1 .
So, when an atom is placed in an external field B , the electron orbit precesses
about the field direction as axis. The electron orbital angular momentum L traces a
cone around the B such that the angle between L & B remains constant
i.e. B B ẑ
and LZ | L |cos
But quantum mechanically, | L | l (l 1) LZ ml
L ml
cos Z (32)
| L | l (l 1)
Thus, angle can have discrete values as ml has (2l 1) possible orientations with
respect to magnetic field. This is known as space quantization
13.7
13.7 Spin-Orbit
Spin-OrbitCoupling
Coupling: :Vector
VectorAtom
AtomModel
Model
The total angular momentum of an atom results from the combination of the orbital
and spin angular momenta of its electrons. The total angular momentum of one
electron atom is given by the vector sum of l and s , i.e. j = l + s .
This leads to the vector model of atom. Since the magnitude of the angular
momentum l of an atomic electron is given by
|l|= l (l+1) (33)
264
and its z-component l z ml
Similarly the magnitude of spin angular momentum s is given by
|s|= s ( s+1) (34)
and its –component s z ms
Total angular momentum j l s . Then, the magnitude and z-component of j are
given by according to usual quantization condition
| j | j ( j 1) (35)
and jz m j
The possible values of m j ranges from j to j in integral steps. We may write
jz l z sz (36)
and m j ml m s (37)
In case of one electron system, there are only two relative orientations possible,
corresponding to
Fig.13.11
j l s so that j l
j l s so that j l
The angular momenta of an atomic electron interacts magnetically, thus known as
spin-orbit interaction. The torque due to l and s exert on each other which cause
265
then to precess uniformly about their resultant j . If no external torque acts on it,
then total angular momentum j is conserved. Thus the angle between l and s
would remain conserved.
Fig. 13.12
| j |2 | l |2 | s |2 2| l | | s |cos( l , s ) (38)
| j |2 | l |2 | s |2
cos( l , s )
2| l | | s |
j ( j 1) l (l 1) s( s 1)
(39)
2 l (l 1) s( s 1)
From the fig. 13.12, it is noted that l and s cannot be parallel or antiparallel to
each other. For a weak external field B , the vector precesses around B and
spatially quantized. However, as B increase, the l and s are uncoupled and
precesses independently around B and spatially quantized independently.
13.8
13.8 Quantum
QuantumNumbers
Numbersfor
forMultielectron
MultielectronAtom
Atom
For a single electron (single valence) atom, letters are used to describe the different
quantum numbers were all small and so was the letters s, p, d, f….. whereas, for a
complete atom, i.e. multielectron system, capital letters are used for various
quantum numbers.
(i) L :– As we have now understood that for a single valence electron system
(Hydrogen atom and alkali metals), the total angular orbital momentum for the
atom is the same as for a single electron. Thus, the value of L is the same as l
266
value, when there is more than one electron in an atom then discrete values of l is
assigned each electron must be added up vectorially to obtain resultant orbital
angular momentum of the atom.
L l1 l2 l3 ....... li (40)
i
If all li ' s are in same direction, L becomes maximum equal to li . The minimum
i
possible value for L could be zero ,but if one of the li ' s is larger than the sum of all
others, minimum value is not zero.
For two electron atom, value of L for the atom is written as
L (l1 l 2 ),(l1 l2 1),(l1 l2 2).......(l1 l2 ) (41)
For example, say l1 2 & l2 1 , than L can have only one of the value 3, 2 or 1.
(see Fig.13.12).
Fig. 13.12
(ii) S :– As we know already that value of spin for each and every electron is ½
which could be either parallel or antiparallel to the preferred direction. Unlike the
case of L , each electron is assigned with a discrete and definite value of spin si and
all si combine to form a resultant S for the atom. For N electrons, possible values
for S can be written as
N N N 1
, 1 , 2 ,....... or 0 (42)
2 2 2 2
The minimum possible value is either ½ if N is odd or zero if N is even.
Fig. 13.13
267
Since L & S are associated with their corresponding magnetic moment and thus
interaction between L and S yields total angular momentum J . The possible
descrete value of J depends upon the possible allowed orientation of L and S .
(iii) J :– In quantum mechanics, total angular momentum of the atom is
essentially the function of J and it is written as J ( J 1) and have certain
discrete values in between
| L S |,| L S 1|.........| L S | (43)
The minimum and maximum values of J are obtained by subtracting and adding
values of L and S .
If L>S, then J can have (2S 1) possible values for a given L and if L< S than J
will have ( 2 L 1) .
13.9
13.9 Spectral
SpectralTerms
Termsand
andTheir
TheirNotations
Notations
The spectral behavior of an element is characterized by the outermost electrons
which are not interlocked in closed shells. To describe the state of electron, small
letters (l,s,j) are used while the capital letters L, S, and J describe the state of
complete atom as whole.
For the case of single electrons system, the value of L, S and J are the same as that
of l, s, and j because inner most electrons do not contribute to the total angular
momentum. The multiplicity of a state is decided by ( 2 S 1) . Thus, for single
1
electron system S . The multiplicity of state is two ,corresponding to the
2
1 1
values L and L – for J in addition to the ground state. But for
2 2
1
multielectron system S can have any value not precise to . For example, three
2
1 1
electron system S or , thus multiplicity of the state is either double or
2 3
quarter except the ground state.
Therefore to describe the state of an atom, it is defined as
nL2j S 1
268
3
For example, the state having j and J then state is defined as 2P32 which
2
clearly illustrates that the value of L is given by the capital letter. Here the values
of n (principal quantum number) is 2. Further, state of the system may also be
defined as
2 S 1
nl x LJ
Where l is the orbital quantum number of electron, i.e., s, p, d, …….. and x is the
number of electrons in that orbital (x is 1 or 2 for s orbital, 1 to 6 for p orbital).
Actually nl x is the configuration of the outermost electrons.
13.10
13.10Description
DescriptionofofGround
GroundState
State
1 1 1
For one electron system, S with respect to L. Thus, J L and L i.e.
2 2 2
1 1
double. But for the ground state L 0 and then J or . We know the
2 2
value of J is given by ( L S ) or ( L S ) and must be positive, thus the possibility of
1
is not allowed. Hence, for a single electron system, ground state is always
2
singlet. Whereas, for mutli-electron system, J S as L 0 for ground state, thus
1 3
J can have any value as S can, i.e. 0, , ...... .If L S , multiplicity of the state is
2 2
given by ( 2 L 1) yield to the possible values of J as one (L= 0) and thus state is
singlet.
13.11
13.11Stern-Gerlach
Stern-GerlachExperiment
Experimentand
andElectron
ElectronSpin
Spin
In 1922, this experiment was performed by O. Stern and Gerlach, which directly
manifest the main features of vector atom model. This experiment demonstrates
that an atom in a magnetic field can take only certain discrete orientations and also
exhibits the existence of electron spin and provides experimental verification of
vector atom model. Since, the atom is considered as a small magnet, where the
magnetism arises due to spin (spin angular momentum) and orbital (orbital angular
momentum) motions of the electrons. When this atomic magnet is placed in a
homogeneous (uniform) magnetic field, i.e. having equal and opposite magnetic
strength, it gets aligned in the direction of magnetic field and does not experience
269
any translatory motion, i.e. the magnet moves in a straight path without any
deviation. But when this atomic magnet is placed in non-uniform magnetic field
,then the magnet not only align along the direction of magnetic field but also have
translatory motion, i.e. the projector is a curved path due to displacement.
Fig. 13.14: The Stern-Gerlach experiment.
The plan of experimental arrangement is shown in Fig. 13.14. The substance of
neutral silver atoms is heated up in an electrical oven. On heating, substance emits
a beam of neutral atoms in all direction and collimated by few slits and then passes
through a non-homogeneous magnetic field. The nonuniform magnetic field is
produced by specially designed pole-pieces, whose cross sectional view is shown
separately. The atomic beam is then made to strike on a photographic plate. The
magnetic field is made more intense and more non-uniform as much as possible.
On developing the photographic plate, none trace of direct beam is observed rather
two traces are obtained which are symmetric with respect to the direct beam. This
implies that the beam is splitted in two discrete directions, one is in +z direction
and other in –z direction. The same has been observed for different atoms.
Interpretation of results:– In the case of silver, a straight line is obtained without
field and double trace with some irregularities is obtained in the presence of field.
The irregularities in double trace occur due to irregularities of magnetic field near
the knife-edge of the poles of magnets.
Some important features of vector atom model can be explained easily.
(a) Spin of the electron:– It was ascertained by using beam of Hydrogen
atoms. The atom consists of single electron in ground state (s-state; l = 0). If there
were no spin then j would also be zero ( j l s) , so that m j ( 2 j 1) 1 implies
that splitting of line will not take place and thus m j g 0 . But it has been found
270
the beam to be splitted in two symmetrically deflected components giving rise to
two traces. This occur when the existence of electron spin is admitted and a value
½ is assigned to spin quantum number. Thus, j l 12 s 0 21 12 so that
2 j 1 2 , then naturally will have two values +1 and –1. Hence, two traces
obtained are in complete agreement with theory.
(b) Quantization of Space: Classically, atomic magnets can orient-themselves
in any direction should give diffused path instead of two distinctly visible traces.
But due to quantization of spin, only certain discrete orientations are permissible.
If we consider silver atom belonging to one electron in its ground state then l 0
and j s , and the possible orientation will be (2 j 1) 2 , i.e. we must get double
trace which shows that the atoms passing through the field become oriented in
space in discrete directions. Therefore H, Na, K, Cu, Ag belong to one electron
system showing the value s 12 , l 0 , for ground state. Then 2 j 1 2 , traces are
possible. Further m j g have +1 and –1, two discrete possible orientations. But in
case of many electron system, number of traces depends upon the value of s . Zn,
Cd, and Hg have 2 s -electrons in their outermost orbit and their normal state is
defined by 1 s0 which mean j 0 . Thus 0 , which means that application of
field brings no effect. In the case of Ni, Co, Fe the effect observed clearly due to
large value of electron spin.
Therefore, Stern-Gerlach experiment not only verifies the main features of vector
atom model but also establishs the fact that diamagnetic substances do not have
resultant magnetic moment while paramagnetic substances do have, which agree
with experimental data.
13.12
13.12Illustrative
IllustrativeExamples
Examples
Example 13.1: An electron is in 2 p state of Hydrogen atom. Find the magnitude
of orbital angular momentum and z-component of l .
Sol: The orbital angular momentum is given by
| l | l (l 1)
and for p-state, l 1 | l | 2
Also z-component of l is defined as
l z ml
271
where ml 1, 0, 1 for l 1 (p state), hence l z , 0 ,
Example 13.2 What are the possible orientation of j for the j 3 2 and j 12
states which correspond to l 1 .
Sol: For any value of total orbital angular momentum I, the possible orientations
aregiven by
m j as j to j .
i.e., for j 3 2 state, m j 3 2 , 12 , 21 , 23
and for j 12 state m j 12 , 12 .
Example 13.3: For one electron atom, calculate | l |,| s |,| j | for a p-electron.
Sol: For electron in p-state l 1, s 12 .
Thus j will have two values:
(i) j l s 1 12 23
(ii) j l s 1 12 21
Therefore | l | l ( l 1) 2
and | s | s( s 1) 3
2
15
| j | j ( j 1) ( 1)
3 3
2 2 for j 32
2
3
( 1)
1 1
2 2 for j 12
2
Example 13.4: Determine the orbital state for n 3, s 12
Sol: For n 3 the corresponding value of l are 0, 1, 2.
1
(i) l 0, s ( l 0 state)
2
1
j l s then corresponding state is 3s 12
2
(ii) l 1, s 12 ( (l 1 p state)
j l s 32 , 12 then corresponding states are 3 p3 / 2 , 3 p1/ 2
(iii) l 2, s 12 ( (l 2; d state)
272
j l s 52 , 32 then corresponding states are 3d5 / 2 , 3d3 / 2
Orbital states are defined by nl 2j s1 , where ( 2 s 1) is known as spin multiplicity.
Example 13.5: What would be the total quantum number j for two electrons with
same l 1 and s 12 .
Sol: l1 l2 1 for both electrons,
then | L | | (l1 l2 ) |,| (l1 l2 1) |........| (l1 l2 ) | 2, 1, 0
Similarly, s1 s2 12 for both electrons
| s | | s1 s2 | | s1 s2 1|.......| s1 s2 |
Then, the allowed values for J are as follows:
(i) L 2, s 1 ; J L S , .....to ......... L S 3, 2, 1
(ii) L 2, S 0 ; J 2
(iii) L 1, S 1 J 2, 1, 0
(iv) L 0, S 1 J 1
(v) L 1, S 0 J 1
(vi) L 0, S 0 J 0
Example 13.6: State 2 s3/ 2 is possible or not?
Sol: For s -state l 0 as s 12 given j l s 12 there 2 s3/ 2 cannot exist, but 2 s1/ 2
can exist.
Example 13.7: Calculate the possible two orientations of spin vector s with
respect to a magnetic field direction.
Sol: s s( s 1) where s 12 and z component of spin angular momentum
s z ms , where ms 12 .
s ms ms
Therefore cos z
3 s ( s 1) s( s 1)
for ms 12 ,
cos1 1
3
0.577 1 54055 '
and cos 2 1
3
0.577 2 12514 '
273
Hence, two possible orientations are 54º55' & 125º14'.
Example 13.8 For the electron is 2D5 / 2 state, calculate (i) possible values of m j
and J Z , (ii) possible orientations of J in vector space.
Sol: For 2D5 / 2 state, l 2 , s 12 and j 52
(i) The possible of m j 52 , 32 12 , 12 , 23 , 25 and z-component of total orbital
angular momentum
J z m j 52 , 32 , 12 , 21 , 32 , 52
(ii) Possible orientation of j in space are given by
mj 2m
cos j
j ( j 1) 35
cos .35, .51, .17 respectively for 52 , 32 , 12
13.13Self
13.13 SelfLearning
LearningExercise
Exercise
Q.1 What is the total angular momentum of an atom?
Q.2 What is Bohr magneton ?
Q.3 For an electron in p3/2 state, find the values of m j and jz .
Q.4 What would be the total quantum number j for electron with l1 1 and
l2 2 .
Q.5 How the different atomic energy levels in atom are designated ?
13.14Summary
13.14 Summary
So far, this unit initializes with the description of Vector Atom model, where the
atom is treated three dimensional entity rather a two dimensional system. Giving
the understanding of the quantization of space and spin, magnetic momenta of the
atom have been described. The behavior of atom in the presence of magnetic field
has been understood with the concept of precession as Larmor’s precession
(frequency). Coupling of spin and angular momentum have been understood in the
Vector Atom model. Extending the idea of coupling for many electrons system has
been summarized. Finally, experimental verification of features of the Vector
Atom model has been studied by Stern – Gerlach experiment.
274
13.15
13.15Glossary
Glossary
Quantization : It is the process of converting a continuous range of values into a
finite range of discreet values.
Orientation : Position or alignment relative to points of the compass or other
specific directions
Moment : It is a combination of a physical quantity and a distance. The moment of
a force is a measure of its tendency to cause a body to rotate about a specific point
or axis.
Precession : It is a change in the orientation of the rotational axis of a rotating
body or the slow movement of the axis of a spinning body around another axis due
to a torque (such as gravitational influence) acting to change the direction of the
first axis.
13.16Answers
13.16 AnswerstotoSelf
SelfLearning
LearningExercise
Exercise
Ans.3: ; jz 32 to 32
m j 32 to 32
Ans.4: L = 4, 3, 2; S = 1, 0.
13.17
13.17Exercise
Exercise
Section A : Very Short Answer Type Questions
Q.1 Why the concept of electron spin was introduced ?
Q.2 Comment on angular momentum conservation.
Q.3 What do you understand by Larmor' precession and Larmor’s frequency ?
Q.4 What is dipole moment ?
Section B: Short Answer Type Questions
Q.5 For a d-electron, find the value of s, l and j .
Q.6 If an electron is in 4d level of hydrogen atom, calculate the magnitude and
orbital angular momentum along with its possible z-components.
Q.7 Obtain the orbital states (term values) for electron with l1 1 and l2 2 .
Q.8 Calculate the possible orientations of the total angular momentum vector j
corresponding to j 3 / 2 with respect to magnetic field.
275
Q.9 A beam of electrons enter a uniform magnetic field of flux density 1.2 Tesla.
Find the energy difference between the electrons whose spin are parallel and
antiparallel to the field.
Q.10 What do you mean by space quantization ? Explain by drawing a suitable
diagram.
Q.11 Discuss the origin of vector atom model.
Q.12 What are quantum numbers ? Explain the significance of each in the theory
of atom.
Section C: Long Answer Type Questions
Q.13 Derive an expression for total magnetic moment of an atomic electron.
Q.14 What do you mean by spinning of an electron ? How the spin electron
coupled with orbital motion of electron ?
Q.15 What are quantum numbers ? Explain the significance of each in the theory
of atom.
Q.16 Obtain an expression for Larmor frequency. Calculate it is the case of
electron when a magnetic field of 104 Weber/m2 is applied to it.
Q.17 Describe Stern-Gerlach experiment neatly. How it verifies the features of
vector atom model ?
Q.18 In Stern-Gerlach experiment, what happens if ions are used instead of
atomic beam is non-homogenous magnetic field ?
13.18
13.18Answers
AnswerstotoExercise
Exercise
Ans.5: For d-electron l 6 ; s 3
2 ; j 35
2
Ans.6: L 6 ; Lz 2 to 2
Ans.8: 392 , 75 ,105 ,140.8
e
Ans.9: Vm B
2m
2 e 1.39104
Energy difference Vm B eV.
2m
e
Ans.17: Larmor frequency f B
4 m
276
e 1.61019 C, m 9.11031 kg, B 104 Weber/m2
f 1.411014 per second.
Ans.18: In Stern-Gerlach experiment, a beam of neutral atom –s is passed in a non
homogeneous magnetic field and each atom experiences a transverse force
depending upon the orientation of applied field. If ions were used, they
would experience Lorentz force instead of transverse force and their
deflection would no longer be transverse and hence no traces would be
obtained.
Referencesand
References andSuggested
SuggestedReadings
Readings
1. Bransden and Joachain, Physics of Atoms and Molecules, (2009), Benjamin
Cummings.
2. Raj Kumar, Atomic and Molecular Spectra: Laser , Kedarnath Ram Nath Pub.
3. S.L. Gupta, V. Kumar, R.C. Sharma, Elements of Spectroscopy, Pragati
Prakashan.
4. Rajam J B, Atomic Physics (2007), S. Chand & Co., New Delhi.
5. S.N. Thakur and D.K. Rai, Atom, Laser and Spectroscopy, PHI Learning Pvt.
Ltd.
6. Fewkes J.H. and Yarwood J. Atomic Physics Vol II (1991) Oxford University
Press.
7. Rita Kakkar, Atomic and molecular spectroscopy, Cambridge University Press
(2015).
8. http://users.aber.ac.uk/ruw/teach/327/lsjj.php
9. http://www.chem.uwimona.edu.jm/courses/RScoupling.html
10. http://physics.nist.gov/Pubs/AtSpec/
11. http://nptel.ac.in/courses/
277
UNIT-14
Spin Orbit Interaction and
Identical Particals
Particles
Structure of the Unit
14.0 Objectives
14.1 Spin orbit interaction
14.2 Quantum mechanical relativistic correction
14.3 Hydrogen fine structure
14.4 Lamb shift
14.5 Illustrative Examples
14.6 Self Learning Exercise-I
14.7 Identical particle exchange symmetry of wavefunctions
14.8 Formulation of Pauli’s principle
14.9 Atomic orbits and the Hund’s rule
14.10 Illustrative Examples
14.11 Self Learning Exercise-II
14.12 Summary
14.13 Glossary
14.14 Answers to Self Learning Exercises
14.15 Exercise
14.16 Answers to Exercise
References and Suggested Readings
14.0
14.0Objectives
Objectives
The fine structure observed in hydrogen spectral lines were first explained by
Sommerfeld. He used the relativistic variation of mass of the electron moving into
elliptic orbits. A more perfect picture of fine structure was given by Quantum
278
mechanics using spin-orbit coupling and taking into account the relativistic
corrections. The current unit describes in detail the spin-orbit interaction and fine
structure of hydrogen spectral lines. The chapter also explains the structure of
multi electron systems.
14.1Spin-Orbit
14.1 Spin-OrbitInteraction
Interaction
The spin-orbit interaction, which is the interaction between electron’s spin angular
momentum S and its orbital angular momentum L is responsible for the fine
structure of the excited states of one electron systems.
If the electron is moving in an electric filed E, the field can be expressed in terms
of a scalar potential V(r) as,
= ( )
Where, r is the distance between the electron and the nucleus.
The orbital motion of the electron with velocity v in the electric field E produces a
magnetic field B, which is given by,
1 1 ( )
= × = ( × )
The orbital angular momentum of the electron L is given by m × , so the
above expression can be written as
1 ( )
=
In terms of electron’s spin angular momentum S, the magnetic potential energy can
be written as
∆ , = −µ .
µ is given by,
µ =− ( )
where =2. Thus the magnetic potential energy in terms of electron’s spin
angular momentum can be written as,
∆ , = .
Substituting for B, we get
279
1 ( )
∆ , = .
This is the expression for magnetic potential energy in a frame where the electron
is at rest. In a frame where, the nucleus is at rest, the energy get reduced by a factor
two. The origin of this factor in the spin orbit Hamiltonian on relativistic
transformation is known as “Thomas precession”. Including the correction factor,
the spin-orbit interaction energy can be written as
1 ( )
∆ , = .
2
The above expression can also be expressed in terms of quantum numbers l, s,and j
=+
. = ( + ). ( + )
. = . + . +2 .
Since . = . ,
. = ( . − . − . )
= ( − − )
ℎ
= [ ( + 1) − ( + 1) − ( + 1)]
2
Substituting the expression for S.L, the expression for spin-orbit interaction energy
can be written as
ℎ 1 ( )
∆ , = [ ( + 1) − ( + 1) − ( + 1)]
16
This is the general expression for spin-orbit interaction energy of an atom. In the
( )
above expression, the average value of has been taken over the
unperturbed motion since it is not constant during the electron motion.
( )
For a given atom, the average value of can be calculated using the
potential function V(r), and the radial probability density.
280
Spin-Orbit Interaction Energy for Hydrogen like Atom
In case of hydrogen atom, the electron moves in a Coulombian field. The potential
energy is given by,
1
( )=−
4
Using this expression for potential in the expression for spin-orbit interaction
energy can be written as
ℎ 1
∆ , = [ ( + 1) − ( + 1) − ( + 1)]
4 (16 )
where the average value of is given as,
1
=
1
+ ( + 1)
2
=4 is the radius of the smallest Bohr orbit of the Hydrogen
atom. Using these, the final expression for the energy reduces to
ℎ
∆ , = [ ( + 1) − ( + 1) − ( + 1)]
1
2 + ( + 1)
2
where, = is known as Rydberg constant, and = = is
known as fine structure constant and is dimensionless.
Now, for a single electron system, =
1
= ±
2
Substituting these values of j in the expression for energy, the energy shift
corresponding to = + and = − can be given as,
ℎ
∆ = [2 + 1]
1
2 + ( + 1)
2
281
ℎ
∆ =
( + 1)
This expression shows that,
Heavier atoms larger spin-orbit coupling
Larger n smaller spin-orbit coupling
14.2
14.2Quantum
QuantumMechanical
MechanicalRelativistic
RelativisticCorrection
Correction
In order to calculate the energy shift, which is due to the relativistic effects, the
relativistic Hamiltonian of the electron with rest mass m0 , can be written as
= +
where = ( + ) − is the relativistic kinetic energy, and
V is the potential energy.
Substituting for K, in the expression for H and after simplification, the expression
for relativistic Hamiltonian can be written as,
=( + ) − +
= − + ⋯……….+
2 8
The first term is the standard non-relativistic expression for kinetic energy. The
second term is the lowest-order relativistic correction to this energy. There the
correction to Hamiltonian is,
1
∆ =−
8
This can be considered as a perturbation term, which using equivalent differential
operator for p, can be written as
1 ℎ
=− −
8 2
1 ℎ
=− ∇
8 16
282
If ψ0 is the unperturbed wavefunction of the hydrogen atom, the first-order energy
shift due to the relativistic correction is given by,
ℎ
∗
16
∆ =− ∇
8
Upon evaluating the integral , the correction in the energy is given as
2 ℎ 1 3
∆ =− −
2 +1 8
where is the Rydberg constant, and α is fine structure constant.
14.3
14.3Hydrogen
HydrogenFine
FineStructure
Structure
The term shift due to spin-orbit interaction is given by,
∆ ,
∆ , =−
ℎ
Thus the net term-shift due to spin-orbit interaction and relativistic effects, which
combine in a liner manner is given by,
∆ , ∆
∆ =∆ , +∆ = +
ℎ ℎ
where the expressions for ∆ , and ∆ has been derived in the previous
sections.
For a single electron system, = , hence for = + = + and
= − = − , the net term shift is given as
1 3
∆ = −
+1 4
and
1 3
∆ = −
4
In terms of j, the two equations can be combined to a single equation:
283
1 3
∆ = −
1 4
+
2
This equation was also obtained by Dirac using quantum mechanical treatment of
hydrogen like atom and hence this equation is also known as Dirac equation.
Sommerfeld’s formula: Sommerfeld also derived a relativistic equation for energy
levels of hydrogen-like atoms.
1 3
∆ = −
4
In his equation + is replaced by .
Comparison of energy levels of hydrogen atom
1
= 1.097 × 10 , = , =1( ℎ )
137
Let us consider Bohr levels corresponding to n=1, 2, 3
Bohr level Sommerfeld levels Dirac levels
n k ΔT (cm-1) l 1 ΔT (cm-1)
= ±
2
1 1 1.46 0 1 1.46
2
2 2 0.091 1 3 1 0.091, 0.456
,
2 2
1
1 0.456 0 0.456
2
3 3 0.018 2 5 3 0.018, 0.054
,
2 2
2 0.054 1 3 1 0.054, 0.162
,
2 2
1
1 0.162 0 2
0.162
284
Fig. 1(a), (b),and (c) shows the energy level for hydrogen atom as predicted by
Sommerfeld and Dirac for levels n=1, 2, and 3. Both the predictions are similar in
case of hydrogen atom.
Fig. 1 (a) Fig. 1 (b)
Fig. 1 (c)
285
Fine Structure of Hydrogen
Effect of the fine structure energy-shift on then=1,2 and 3 states of
hydrogen atom.
For n=1, in the absence of fine structure, there are two 1S1/2 states. The fine
structure induced energy shift is same for both the states. Hence fine structure
doesn’t break the degeneracy of this state of hydrogen atom.
For n= 2, there are two 2S1/2, two 2P1/2, and four 2P3/2 states. All these states are
degenerate. Fine structure breaks the degeneracy of the states relative to 2P3/2.
For n=3, there are two 3S1/2 , two 3P1/2 , four 3P3/2 , four 3D3/2 , and six 3D5/2. All of
these states are degenerate. Fine structure breaks these states into three groups:
3
S1/2 , and 3P1/2 , 3P3/2 , 3D3/2 , and 3D5/2 states.
14.4
14.4Lamb
LambShift
Shift
The Dirac theory applied to hydrogen-like atoms predicts that the energy levels of
the hydrogen electron should depend only on the principal quantum number n.
Hence the states with same n , and the same total angular momentum quantum
286
number j are degenerate. Thus, according to Dirac theory, the 22P1/2 and 22S1/2 states
of hydrogen are degenerate. However it was found that 22P1/2 was lower than 2
2
S1/2. This effect was first measured by Lamb and Rutherford in 1947 in the
experiment on the hydrogen microwave spectrum. They showed that for hydrogen-
like atoms states of particular n, having same j but different l values are not
degenerate but separated. The shift of the 22S1/2 level above the 22P1/2 level is called
Lamb shift.
Measurements of Lamb shift:
The Lamb shift is extremely small and is difficult to measure as a splitting in the
optical or uv spectral lines. However it is possible to make use of transitions
directly between the sublevels by going to other regions of the electromagnetic
spectrum. Willis Lamb made his measurements of the shift in the microwave
region. He formed a beam of hydrogen atoms in the 2s(1/2) state. These atoms could
not directly take the transition to the 1s(1/2) state because of the selection rule which
requires the orbital angular momentum to change by 1 unit in a transition. Putting
the atoms in a magnetic field to split the levels by the Zeeman effect, he exposed
the atoms to microwave radiation at 2395 MHz (not too far from the ordinary
microwave oven frequency of 2560 MHz).
Then he varied the magnetic field until that frequency produced transitions from
the 2p(1/2) to 2p(3/2) levels. He could then measure the allowed transition from
the 2p(3/2) to the 1s(1/2) state. He used the results to determine that the zero-
287
magnetic field splitting of these levels correspond to 1057 MHz. By the Planck
relationship, this energy separation was about 4.372 ×10-6 eV.
Significance of the Lamb Shift
When the Lamb shift was experimentally determined, it provided a high precision
verification of theoretical calculations made with the quantum theory of
electrodynamics. These calculations predicted that electrons continually exchanged
photons, this being the mechanism by which the electromagnetic force acted. The
effect of the continuous emission and absorption of photons on the electron g-
factor could be calculated with great precision.
The tiny Lamb shift, measured with great precision, agreed to many decimal places
with the calculated result from quantum electrodynamics. The measured precision
gives us the electron spin g-factor as
g=2.002319304386
14.5Illustrative
14.5 IllustrativeExamples
Examples
Example 1: If the doublet splitting of the first excited state 22P3/2-22P1/2 of He+ is
5.84 cm-1. Calculate the corresponding separation for H.
Sol: The doublet splitting of a one-electron atomic state arising due to spin-orbit
interaction is given by
∆
∆ = =
ℎ ( + 1)
where is Rydberg constant, α is fine structure constant, and Z is atomic
number.
For a given state (n, l constant), ∆ ∝
For He+, Z=2 and for H, Z=1. Hence,
∆ (2)
= = 16
∆ (1)
1
∆ = ∆
16
1
∆ = × 0.584
16
∆ = 0.365
288
14.6
14.6Self
SelfLearning
LearningExercise-I
Exercise-I
Q.1 What is the significance of quantum number J ?
Q.2 What J is equal to ?
Q.3 What is Rydberg constant ?
Q.4 What is the value of fine structure constant ?
Q.5 The doublet splitting of the first excited state 2P3/2- 2P1/2 of H atom is
0.365 cm-1. Calculate the corresponding separation for Li++.
14.7Identical
14.7 Identical Particle
ParticleExchange
exchange Symmetry
Symmetry of
of Wavefunctions
Wavefunctions
Identical particles: A system is said to be consist of identical particles if on
interchanging the position and co-ordinates of any two particles there is no way to
know that a change has been made in the system.
In classical description of system containing identical particles, a label can be
assigned to identical particles. For e.g., in a box containing electrons, the electrons
can be labeled as a and b. While the electrons travel in their well-defined
trajectories, at any given instance it can be told that which electron is a and which
electron is b. However, in a quantum mechanical description it will not be possible
as the uncertainty principle doesn’t allow us to observe the motion of the electron
without disturbing the system. Though it can be stated that at a given point of time
an electron was located but not which electron it was. In other words, due to the
overlapping of the wavefunctions of the two electrons, it is impossible to say
which wavefunction was associated with which particle. Therefore, the
indistinguishability of identical particles must be taken into account in the quantum
mechanical description of identical particles.
Consider a system of two electrons. The Hamiltonian for the system can be written
as = + where Ha , and Hb are the hamiltonians for the individual
electrons.
The wavefunction for the system can be written as the product of the individual
wavefunctions.
( , )= ( ) ( )
If the electron a is in state 1, and electron b in state 2, then the total wavefunction
can be written as
( , )= ( ) ( )
289
= ( ) ( )
The probability density function for this system will be
∗ ∗ ∗ ( ) ( )
= ( ) ( )
On interchanging the states i.e. electron a is in state 2, and electron b in state 1, the
total wavefunction will be,
= ( ) ( )
The probability distribution function for this new arrangement would be
∗ ∗ ∗ ( ) ( )
= ( ) ( )
Since the electrons are indistinguishable, changing the labels should not change
any of the physically measurable quantity. If we change the labels in ∗ , then
∗ ∗ ( ) ( )→ ∗ ∗ ( ) ( )
( ) ( ) ( ) ( )
This interchange leads to the distribution function ∗ which is different than
∗
. Thus merely changing the labels of the electrons resulted into the change
of the probability density. Hence for a two electron system, the wavefunctions
described above doesn’t properly represent the system.
Consider a system of N particles. Let us say that the total wavefunction of the
system is ψ(a,b,…..N). As we know that the Hamiltonian of a system is invariant
with respect to the position and spin of the particles, let us consider an operator Cab
, whose action is to interchange the coordinates of any two particles. i.e.
Cabψ(a,b,…..N)= ψ(b,a…..N)
Cab is also linear like parity operator.
Cab ψ=αψ
where α is the eigenvalue. Operating once more,
=
By definition, the operator after two operations brings back the system into the
original state. Hence
=
So that =1
Or, α=±1
Thus, Cabψ(a,b,…..N)=± ψ(a,b…..N)
On comparison we get,
290
ψ(b,a,………..N)=± ψ(a,b,………..N)
Thus if the two particles of the system are changed, the wavefunction either remain
unchanged or changes its sign. Thus with respect to the exchange of the particles,
the wavefunctions are either symmetric or antisymmetric.
The particles, which can be described by symmetric wavefunction are known as
bosons . Thus for a boson,
ψ(a,b,………..N)=+ ψ(b,a,………..N)
All particles having integer spins are bosons.
The particles which can be described using antisymmetric wavefunction are known
as fermions. Thus for a fermion
ψ(a,b,………..N)=- ψ(b,a,………..N)
Particles having half-integral spin are known as fermions. Electrons are fermions.
14.8
14.8Formulation
FormulationofofPauli’s
Pauli’sPrinciple
Principle
Wolfgang Pauli, in 1925, gave his exclusion principle to explain the arrangement
of electrons in an atom according to which, “no two electrons in an atom can have
identical quantum numbers”. This is an example of a general principle which
applies all the particles having half-integer spin (fermions). It does not apply to
particles of integer spin (bosons).
Consider a system of two identical and non-interacting particles a, and b. The total
Hamiltonian of the system can be written as,
= +
Where Ha , and Hb are Hamiltonians for separate particles. The wavefunction for
the two electron system would be
( , )= ( ) ( )
If the particle a is in quantum state 1,and particle b is in quantum state 2, then the
combined wavefunction of the system is
( , )= ( ) ( )
If the particles exchange their respective states, the new wavefunction would be
( , )= ( ) ( )
Since the particles are identical and indistinguishable, both and will
291
equally describe the system. Hence a linear combination of these two will be more
appropriate to describe the system. Thus
1
( , )= [ ( ) ( ) ± ( ) ( )]
√2
where, is the normalization factor. With the exchange of co-ordinates, this
√
wavefunction is either symmetric (+ sign) or ant symmetric (-sign).
Symmetric ( , ) = [ ( ) ( ) + ( ) ( )]
√
Antisymmetric ( , )= [ ( ) ( )− ( ) ( )]
√
Thus, if both the particles are in same state,
( , )≠0
( , )=0
Thus, no two fermions can occupy the same quantum states. It can be stated as, in
a multi-electron system, it is impossible for two electrons to have the same values
of all the quantum numbers. Another statement is that, with respect to the exchange
of the particles, the total wavefunction for two identical fermions is
antisymmetric. This means that the wavefunction changes its sign if the space and
spin co-ordinates of any two particles are interchanged. In other words, it can also
be stated as if two particles are described by antisymmetric wavefunction, they
cannot occupy the same quantum state. Thus a multielectron system must be
described by an antisymmetric wavefunction.
14.9Atomic
14.9 AtomicOrbits
Orbitsand
andthe
theHund’s
Hund’sRule
Rule
Filling of subshells having more than one orbital are done according to the Hund’s
rule. In 1927 Hund formulated two empirical rules.
Hund’s rule -I: Of the states arising from a given electron configuration, the
lowest in energy is the one having highest multiplicity. In other words, electron
pairing will not take place in orbitals of same energy (same sub-shell) until each
orbital is first singly filled with parallel spin. This is known as Hund’s rule of
maximum multiplicity.
Hund’s rule -II: For a given multiplicity, the lower in energy is the one with
higher L value.
292
In the process of assigning the electrons to an orbital, the electron first fill all the
orbitals having same energy before it pairs with another electron in a half-filled
orbital. The atoms in their ground states tend to have as many unpaired electrons as
possible.
For Example : Nitrogen Atoms
Consider the correct electron configuration of the nitrogen (Z = 7) atom: 1s2 2s2 2p3
The p orbitals are half-filled; there are three p orbitals and three electrons. This is
because the three electrons in the 2p subshell will fill all the empty orbitals first
before pairing with electrons in them.
Hund's Rule Explained
According to the first rule, an electron first fills an empty orbital before it decides
to pair up. Negatively charged electrons repel each other. Hence to minimize the
repulsion, electrons tend to occupy their own orbitals rather than sharing an orbital
with another electron. Furthermore, the calculations have shown that the electrons
in singly occupied orbitals are less effectively screened or shielded from the
nucleus.
For the second rule, unpaired electrons in singly occupied orbitals have the same
spins. Once the spin of the first electron in a sublevel is chosen, however, the spins
of all of the other electrons in that sublevel depend on that first spin.
Example: Carbon and Oxygen
Consider the electron configuration for carbon atoms: 1s22s22p2: The two 2s
electrons will occupy the same orbital, whereas the two 2p electrons will be in
different orbital (and aligned the same direction) in accordance with Hund's rule.
Consider also the electron configuration of oxygen. Oxygen has 8 electrons. The
electron configuration can be written as 1s22s22p4. To draw the orbital diagram,
293
begin with the following observations: the first two electrons will pair up in the 1s
orbital; the next two electrons will pair up in the 2s orbital. That leaves 4 electrons,
which must be placed in the 2p orbitals. According to Hund’s rule, all orbitals will
be singly occupied before any is doubly occupied. Therefore, two p orbital get one
electron and one will have two electrons. Hund's rule also stipulates that all of the
unpaired electrons must have the same spin. In keeping with convention, the
unpaired electrons are drawn as "spin-up"..
14.10
14.10Illustrative
IllustrativeExamples
Examples
Example 1: Show that the total number of electrons in a shell is 2n2, where n is the
principle quantum number of the shell.
Sol: To define the state of an electron, we need a set of four quantum numbers:
n, l,ml, and ms.
For a given n, the azimuthal quantum number l, can take values
l=0,1,2,3……n-1
For each l,ml can take values:
ml= -l,…0,…..+l
that is a total of (2l+1) values. For each of these values, the magnetic spin quantum
number ms, can be either +1/2 or -1/2. Thus for a given l, there are 2(2l+1) sets of
quantum numbers. Summing over all the possible values of l, for a given n, the
number of the possible sets of quantum numbers l, mi, ms,
2(2 + 1)
=2[1+3+5+7+…………………………2(n-1)+1]
=2[1+3+5+7+…………………………2n-1]
=2 × [1+2n-1] = 2
14.11
14.11Self
SelfLearning
LearningExercise-II
Exercise-II
Q.1 Calculate the energy of transition involving n1=6 to n2=3 in a hydrogen
atom.
Q.2 What are the ground state configuration of
(a) Ar (b) K (c) Cl
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Q.3 State Hund’s rule.
Q.4 Calculate the wavelength of first line in Lyman series of hydrogen spectrum.
Q.5 What transition in the hydrogen spectrum would have the same
wavelength as the Balmer transition n = 4 to n= 2 of He+ spectrum ?
14.12
14.12Summary
Summary
The current unit summarizes the observed fine structure in hydrogen spectral lines.
The quantum mechanical description of spin-orbit interaction has been discussed in
detail. The model by Sommerfeld uses classical mechanics to evaluate the energy
shift while the theory by Dirac has used quantum mechanical description. The
theory by Dirac predicted a double-degeneracy of most levels. The fine structure of
Hα lines has also been discussed. A quantum mechanical description of multi-
electron systems and Pauli’s exclusion principle has also been discussed in detail.
14.13
14.13Glossary
Glossary
Shell : Orbitals with same value of the principal quantum number n comprise a
shell.
Energy level : In an atom a location or orbital above the ground state in which an
electron is found when it gains a specific amount of energy.
Energy-level diagram : A diagram showing the arrangement of an atom's energy
levels.
Excited state : A state of an atom ion or molecule with a higher energy than the
ground state.
Balmer line : An emission or absorption line in the spectrum of hydrogen caused
by an electron transition between the second and higher energy levels.
14.14Answers
14.14 AnswerstotoSelf
SelfLearning
LearningExercises
Exercises
Answers to Self Learning Exercise – I
Ans.1: In lighter elements, spin-orbit coupling is small, while in heavier elements
it is large. Hence the new quantum number j becomes important. This
quantum number gives the total angular momentum.
Ans.2: j=l+s
Ans.3: See section 14.1.
295
Ans.4: Fine structure constant α=1/137
Ans.5: 29.6 cm-1
Answers to Self Learning Exercise – II
Ans.1: -1.819×10-19 J
Ans.2: (a)1s2 2s2 2p6 3s2 3p6
(b)The abbreviated electron configuration for potassium is: K [Ar] 4s1
(c)The configuration for chlorine is: Cl 1s2 2s2 2p6 3s2 3p5.
Ans.3: See section 14.9
Ans.4: 1215 A0.
Ans.5: The transition n2=2 to n1=1 (Lyman series) in hydrogen atom has the same
wavelength as the Balmer series transition n2=4 to n1=2 of of He+
spectrum
14.15
14.15Exercise
Exercise
Q.1 Calculate the spin-orbit interaction splitting of a level corresponding to n=2
and l=1 of hydrogen atom.
Q.2 Show that f orbital can accommodate 14 electrons ?
Q.3 A state is denoted as 4D5/2. What are its values of l,s,j.
Q.4 The numerical value of the first orbit of hydrogen is ?
Q.5 What is the value of Rydberg constant for hydrogen ?
14.16
14.16Answers
AnswerstotoExercise
Exercise
Ans.1: 0.365 cm-1
Ans.2: See section 14.10 Example 1.
Ans.3: s=3/2, l=2, j=5/2
Ans.5: See section 14.1.
References
Referencesand
andSuggested
SuggestedReadings
Readings
1. C. N. Banwell and E. M. McCash, Fundamentals of Molecular Spectroscopy,
4thEd., Tata-McGraw-Hill, 1994.
2. G. Aruldhas, Molecular Structure and Spectroscopy ,PHI Learning Pvt. Ltd.,
01-Feb-2004
3. H. S. Randhawa, Modern Molecular Spectroscopy, McMillan India Ltd., 2003
296
UNIT-15
LS & jj Couplings
Structure of the Unit
15.0 Objectives
15.1 Introduction
15.2 Coupling Scheme
15.2.1 Russell – Saunders (LS) Coupling
15.2.2 jj- Coupling
15.3 Selection Rules for Two Valence Electrons
15.4 Terms in Many Electrons System
15.4.1 Terms due to LS- Coupling
15.4.2 Terms due to jj- Coupling
15.5 Terms in Equivalent Electrons
15.5.1 LS- Coupling
15.5.2 jj- Coupling
15.6 Hund’s Rules
15.7 Lande’s Interval Rule
15.8 Normal and Inverted Terms
15.9 Order of Fine Structure Multiplets
15.9.1 LS- Coupling
15.9.2 jj- Coupling
15.10 Selection Rules for Many Electrons System
15.10.1 Selection Rules for LS- Coupling
15.10.2 Selection Rules for jj- Coupling
15.11 Illustrative Examples
15.12 Self Learning Exercise
297
15.13 Summary
15.14 Glossary
15.15 Exercise
References and Suggested Readings
15.0
15.0Objectives
Objectives
In the following discussion, we will study the characteristics, namely, the
spectra of elements, that have two or more than two electrons in their valence shell,
for which one has to follow the various coupling schemes, as these facilitate the
understandings of possible transitions occur in between the filled/half filled shells.
Thus, the possibilities and effects of LS- and jj- couplings will be of our main
discussion as these have direct consequences in the atomic spectra. New Terms
(states) arise after the various interactions, are of great importance, have been
explained. Further, some restrictions, namely, selection rules, Hund’s rules, and
Lande’s interval rules are important to study the exact behavior of atomic
transitions and thus experimental spectra, thus have been paid attention.
15.1
15.1Introduction
Introduction
The spectra of elements (Be, Mg, Ca, Zn, Sr, Ba, Cd and Hg ) resemble
with the spectrum of He in same way. During the excitation of atoms, the
excitations of either single electron or both electrons are possible resulting into the
spectra. Due to two valence electrons, the choice for the transition increases and
therefore, we obtain a large number of spectra lines of these alkaline-earth
elements. The series, like principal, sharp, diffuse and fundamental are observed,
where one corresponds to singlet and other belongs to triplet. It has been found that
energy levels are also influenced when a single electron transition takes place
between these, which is not the same as in the case of alkali elements. To
understand the spectra of alkaline earths, it was proposed that, (i) all s vectors ,all l
vectors are strongly coupled individually with little effect of s vector on l vector
individually, and (ii) the s vector of single electron combined with l vector of same
electron to give j with negligible influence on other electrons and thus, finally we
get single resultant J. The wide spectrum containing number of lines is obtained
when suitable selection principle is applied to the quantum number J. Therefore,
298
we get the resultant vectors S, L and J which are governed by the selection
principles.
15.2
15.2Coupling
CouplingSchemes
Schemes
The atoms may have two or more electrons with different orbital and spin
momenta, therefore there are many ways in which the angular momenta associated
with the orbital and spin motions in many-electron-atoms can be combined
together and varied. The interactions that can occur are of three types. (note: A
brief about the coupling has been discussed in the section 13.7 & 13.8)
(a) Orbit-Orbit (l-l) coupling :
For any electron in the atom, potential energy of repulsion is similar in magnitude
to that due to the attraction by the nuclear charge. Under the assumption, each
electron is described with orbital quantum number li that can have certain discrete
values. Resultant angular momentum of an atom, which in turn will also have
discrete values, is obtained by vector addition of the individual li yielding its value
that depends on the number, the magnitude & direction of each of the electron’s
angular momentum.
For two valence electrons atom, resultant angular momentum is
given by L li (termed as ll- or orbit-orbit coupling) with maximum value
when all the moments are in the same direction, i.e.
L (l1 l2 ), (l1 l2 1), (l1 l2 2)............, l1 l2 . Further, the electrons do influence
one another’s motion and thus this interaction has the effect that l ’s are no longer
constant in time; rather possesses precessional motion about the resultant
analogous to the precession of l and s about their resultant j. Stronger the
interaction, greater will be the precessional velocity of the electrons which is
reflected in the separations of different values of L (Terms of an atom). The Terms
having L 0,1, 2,3, 4...... are designated as S, P D, F…. respectively. In general, the
term values for various configurations of two electron system are given below:
l1 l2 Electrons L Term Symbols
0 0 s, s 0 S
0 1 s, p 1 P
0 2 s, d 2 D
1 1 p, p 2, 1, 0 D, P, S
299
1 2 p, d 3, 2, 1 F, D, P
2 2 d, d 4, 3, 2, 1, 0 G, F, D, P, S
For three electrons system, vector addition of each of L (derived taking two
electrons) is taken with l of third electron to obtain the final states/ Terms.
(b) Spin-Spin (s-s) coupling :
Electrostatic forces, apart from the orbital motion, also affect the spin
motion of electrons. As in the case of orbital angular momentum, one can obtain
the resultant spin of the atom by taking that spins of the individual electrons in an
atom, are either parallel or antiparallel to one another. The resultant spin motion of
a system of several electrons is derived exactly the same way as for the orbital
angular momentum; that is by taking vector addition of individual spin angular
momentum, S si (termed as ss- or spin-spin coupling). Since spin angular
momentum of individual electron can be 12 , their resultant, S will also have
only discrete values with maximum when all the spins are in the same direction
and minimum of 0 or 1/2, respectively depending upon whether the number of
electrons is even or odd.
The electron spins in helium can be either (anti-parallel) or (parallel)
giving S = 0 or 1, respectively. So is the case with all two valence electrons
systems. Obviously, there will be two different Term series, one with S = 0 and
second having S = 1. In three electrons system, spin directions can be or
and or . As the electrons are indistinguishable, first three combinations
yield S = 1/2 and the fourth gives S = 3/2. The magnitude of the resultant spin is
given by S ( s1 s2 ),( s1 s2 1),( s1 s2 2)............, s1 s2
(c) Spin-Orbit (s-l) coupling: This occurs between the resultant spin and orbital
momenta of an electron which gives rise to J, the total angular momentum
quantum number.
Mainly, there are two principal coupling schemes used:
(i) Russell-Saunders or LS- coupling
(ii) jj- coupling
15.2.1 Russell-Saunders (LS) Coupling:
The orbital angular momenta of the electrons are coupled to give a total orbital
angular momentum L li and (ii) The spins of the electrons are coupled to give
300
a total spin S si . Strong coupling of l’s and s’s is electrostatic in nature. In
addition to these electrostatic forces, there are magnetic forces, one due to orbital
motion of the electrons and another caused by their spin motions. These motions
about their respective resultants provide the magnetic moments ( L because of
orbital and S due to spin motions). These two interact weakly. One may visualize
as if a small magnet of magnetic moment S is subjected to an internal magnetic
field of magnetic moment L . This weak interaction will make L and S to precess
around their resultant, J. Therefore, like that of the precession of l and s about their
resultant j, the relative motion of L and S is governed by their resultant which
remains not only fixed in space but also constant in time. That is, L and S perform
precessional motion together as a rigid body about their resultant J. The
combination of a particular S value with a particular L value comprises a
spectroscopic term, the notation for which is 2 s1 L . The quantum number 2S + 1 is
the multiplicity of the term. The S and L vectors are coupled to obtain the total
angular momentum, J = S + L, for a level of the term; the level is denoted as 2 s1 L j
. J will be an integer (0,1,2,3…) when S is an integer for even number of electrons
and J will be an half integer (1/2, 3/2, 5/2, …..) when S is a half integer for odd
number of electrons. Coupling of l ’s to L and s’s to S and finally the coupling of L
and S to yield the resultant angular momentum J is termed as LS- coupling or
Russell- Saunders coupling, shown below.
For example, an atom with only one electron in ground state (l = 0), L will
have only one value 0, since the value of S is ½ and thus J = +1/2. While for an
atom having two electrons such that one with l = 0 and other in excited state with
l = 1, then L l1 l2 an S s1 s2 gives: L = 1 and S = 1 (if electron spins are
parallel) or L = 1 and S = 0 (if electron spins are anti-parallel).Therefore, J = 0, 1, 2
are designated by 3 P0 , 3 P1 , 3 P2 , i.e. P state is splitting into triplet.
301
Possible number of ways in which L and S may combine give rise to the J values
(non negative) are (2 S 1) if L>S and (2 L 1) if L<S. This type of coupling is
commonly used in explaining the spectra of second group.
In this coupling scheme, it is assumed that: spin-spin coupling > orbit-orbit
coupling > spin-orbit coupling. It is a good approximation for lighter atoms (say up
to atomic number 30 or so); for higher atomic number spin-orbit coupling is more
prominent leading to jj- coupling scheme
15.2.2 jj- Coupling:
Consider a two valence electrons atom, one with quantum numbers l1 and
s1 and the second with l2 and s2 . Different types of interactions among the four
quantum numbers are possible. First, l1 interacts strongly with l2 yielding L and s1
with s2 leading to S; finally L couples weakly with S to form LS-coupling. Second
possibility, though rare one, is l1 may interact with spin s2 of the other electron
and l2 with spin s1 of the first. Such inter electrons interactions are very weak to
observe; therefore will not be considered. Third possibility is predominant &
frequent in heavy atoms (large volume) where the electrons are situated at larger
distances and the electrostatic interaction among them diminishes in comparison
with the interaction of individual electron’s orbital motion with its own spin
motion. Thus, l1 interacts strongly with its own spin s1 ( j l s ) leading to
resultant angular momentum j1 of one electron and l2 with its own s2 to yield j2
for the second electron; finally j1 couples weakly with j2 to form jj-coupling. The
total angular momentum of the atom is given by J ji . Therefore, for two
valence electrons atom J ( j1 j2 ),( j1 j2 1),( j1 j2 2)............, j1 j2 . The
coupling scheme is shown in the next figure , where LS- coupling, i.e. orbital and
spin angular moments are combined horizontally, then vertically jj- coupling,
302
i.e. orbital and spin angular moments are combined vertically, then horizontally.
15.3
15.3Selection
SelectionRules
Rulesfor
forTwo
TwoValence
ValenceElectrons
Electrons
If two electrons contribute in producing the spectra then only those
transitions are allowed in which two electrons jump with the emission of radiations
of single frequency. On the other hand if only one electron transits ,then value of l
changes by unity and of other does not change and if both electrons transit such
that l values change by unity and the other does not change or change by two. In
these two types of coupling due to other terms, additional conditions are also
required-
(i) In L-S coupling: L 0, 1 ; S 0 ; J 0, 1 ( 0 0 not allowed).
(ii) In j-j coupling: j1 0 ; j2 0 or 1 ; and J 0, 1 ( 0 0 not allowed).
Quantum mechanically, even terms combine with odd terms and odd terms
combine with even terms. The even terms are those for which l1 l2 = even and
others are odd.
It has been observed that presence of extra electrons other than valence
electrons, the spectra become complicated (e.g. spectra of Hg is more complicated
than of He). As the number of more than two electrons increases, the complexity
increases because of number of terms arises due to various combinations of spin
and orbital vectors. In complex spectra, in addition to ordinary series of singlet,
doublet and triplet, there exists a multiple level of series like four, five, six, seven
or eight with equal spaced. Experimentally, it has been found that these levels are
either all or all odd in the spectrum.
Following table lists resultant spin quantum number and the possible
multiplicities for various numbers of electrons.
303
No. of Electrons Spin Values Possible Mulitplets (2S+1)
1 1/2 2 (Doublet)
2 0,1 1 (Singlets), 3 (Triplets)
3 ½, 3/2 2(Doublets), 4 (Quartets)
4 0,1,2 1 (Singlets), 3 (Triplets), 5 (Quintets)
5 ½, 3.2, 5/2 2 (Doublets), 4 (Quartets), 6 (Sextets)
15.4Terms
15.4 TermsininMany
ManyElectron
ElectronSystem
System
Due to the contribution of additional terms, the atoms have been classified
broadly into two categories: the one, in which spin-spin correlation as deciding
factors has LS- coupling, and the other class in which spin-orbit interaction
predominates has j-j coupling.
15.4.1 Terms due to LS- coupling:
To find out the possible terms, Branching rule is used according to which if
the atom is ionized completely, the electrons return to it one after the another to
form a neutral atom. Thus, the possible spin combinations can be found out.
We can understand this by considering an atom having three valence electrons in
following way:
(i) Consider an atom having three valence electrons like 2s 3p 4d.
(ii) To find the possible values of S, spin of two electrons are combined first and
the third electron is allowed to combine with each of them. From the above
branching scheme, two sets of doublet ( S 1/ 2 ) states and one set of quartet
( S 3 / 2 ) are observed.
304
(iii) For the L values, first combining the orbital motions of first two electrons and
then combined the third one with each of them. Combination of first two p
states results (l + 1) to (l - 1) values, i.e. 2, 1, 0, known as terms S, P, D.
(iv) Now, third d electron is added to these three terms as
S d 022 D
P d (2 1) to (2 1) 3,2,1 F , D, P
D d (2 2) to (2 2) 4,3,2,1,0 G , F , D, P , S
(v) Finally, introducing LS- coupling gives rise to J states, i.e. J LS .
The two sets of doublet will have the following states-
2
D3/2,5/2
2
F5/2,7/2 , 2 D3/2,5/2 , 2 P1/2,3/2 ,
2
G7/2,9/2 , 2 F5/2,7/2 , 2 D3/2,5/2 , 2 P1/2,3/2 , 2 S1/2 ,
i.e. total 34 terms. In quartet set, the following we have
4
D1/2, 3/2, 5/2,7/2 ,
4
P1/2, 3/2, 5/2 4 D1/2, 3/2, 5/2,7/2 4 F3/2, 5/2, 7/2,9/2 ,
4
S3/2 4 P1/2, 3/2, 5/2 4 D1/2, 3/2, 5/2,7/2 4 F3/2, 5/2, 7/2,9/2 4G5/2, 7/2, 9/2,11/2 ,
i.e. in all 31 terms. Thus, total 65 distinct levels.
15.4.2 Terms due to jj- coupling:
Here we consider only the addition of one electron to parent system,
generated with one or more valence electrons. Meaning of parent system is, the
energy level of an ionized atom to which we add another electron via. jj- coupling
to form new energy level for neutral atom.
Let us understand this with a simple example. Consider a parent system
having sp configuration and we are going to add p electron to this system. Possible
terms of parent system are as follows:
l1 s1 j1 1 / 2
l2 s2 j2 1/ 2, 3 / 2
Thus, J j1 j2 1, 0, 1, 2 . Now, then adding up the p electron has j values ½ or
3/2 to these and thus the final total 18 terms will have the following J values.
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15.5
15.5Terms
TermsininEquivalent
EquivalentElectron
ElectronSystem
System
15.5.1 LS- Coupling:
We understand this by the following cases-
(i) Two s- electrons (Unexcited He atom): Here we have l1 0 , l2 0 and
s1 1/ 2 , s2 1 / 2 . To know the possible terms, following the same procedure as
outlined in section 15.5.1, the spin combination results to S = 0 and 1, for which
there is only one possible L value, i.e. L 0 . Thus the terms are 3 S1 and 1 S 0 . Let as
assume that if the electrons have principal quantum number n 1 and n 2 , i.e.
one electron is in excited state then the lowest existing state will be 3S1 . But for the
unexcited state, two electrons will be completely in same structure and thus
become indistinguishable, the ground state of helium atom is 1S0 .
(ii) Two p- electrons (Unexcited carbon atom): Very first, let us consider the
case of two non-equivalent pp- electrons, i.e. say np and np ' . The following
calculation give rise to the possible terms-
l1 1, l2 1 L 2,1,0 and s1 s2 1/ 2 S 1,0
Therefore, the Terms are: 3 D, 3 P , 3 S (triplets) and 1 D, 1 P , 1S (singlets); six in
all. J values for each of the triplet and singlet states are:
306
For 3 D, J 3,2,1 ; Terms are 3 D3 , 3 D2 , 3 D1 ( 3 D3,2,1 ) . Each will have
slightly different energy. For 3 P , J 2,1,0 ; Terms are 3 P2 , 3 P1 , 3 P0 ( 3 P2,1,0 ) . Each
will have slightly different energy. For 3 S , J 1 ; Term is 3 S1 . It may be written as
3 1 1 1 1
S since J is equal to S. For D, J 2 , Term is D2 ; For P , J 1 , Term is P1 ; For
1
S , J 0 , Term is 1S0 . Like in triplets case, J value of the singlet S is not usually
written.
Now we switch over to the case of the equivalent pp- electrons, then
the Pauli’s principal restricts the combination which have the same set of quantum
numbers. Whereas, for non-equivalent electrons, values of n & or l are different
implying that Pauli’s principle is satisfied. However, when n and l are same then
ml and or ms must have different values to meet the requirements of Pauli’s
Exclusion principle. By doing so, some of the states which are possible for the
non-equivalent electrons may not exist for the equivalent electrons. Thus, in our
case, each of the two p electrons has ml 1,0, 1 and can have ms either +1/2 or
-1/2. Therefore, each of the ml values can have ms either +1/2 or -1/2. Values are
tabulate below labeling with a, b, c, d, e, f.
ml 1 0 -1 1 0 -1
ms ½ ½ ½ -½ -½ -½
a b c d e f
If two p equivalent electrons exist, the number of possible combinations out
of the six different columns taking two at time is 6C 2 {(62)!6! 2!} 15 , which are
ab, ac ,ad, ae, af;
bc, bd, be, bf;
cd, ce, cf;
de, df;
ef.
This means that out of 36 magnetic field levels only 15 strong field levels
exist when the electrons are two p electrons. Further, we have to calculate the
values of M L , M S , and M J for which the energy levels are excluded according to
Pauli’s principal. Thus, these possible combinations provide the following values
of M L , M S , and M J .
307
ML 1 0 2 1 0 -1 1 0 -1 0 -1 -2 1 0 1
MS 1 1 0 0 0 1 0 0 0 0 0 0 -1 -1 -1
MJ 2 1 2 1 0 0 1 0 -1 0 -1 -2 0 -1 -2
Group = = | | | = = __ | = = | = = =
Starting with the highest value of M L and according to quantization
rule, it should be equal to the highest value of L. Maximum value of M L is 2 with
M S . Since M L being space quantized value of L, value of L must therefore be 2,
representing possibly 1 D2 term. If this is so, there must be combinations
M L 1,0, 1, 2 each having M S = 0. All these are shown in dark boxes (indicated
by | in the last row). Then there are three groups of M L 1,0, 1 ; where the largest
value of M L is +1 and largest value of M S is +1 ,then they must belong to 3 P state
and for the value of M L is 0 and -1 ,the M S has +1, 0 and -1 which correspond to
3
P state (indicated by = in the last row). Further, the remaining term has M L = 0
and M S = 0 belongs to 1 S 0 state (indicated by – in last row). The number of states
is reduced to three 1 D2 , 3 P , 1 S 0 as against the six for the two non-equivalent p
electrons.
Terms of equivalent electrons can easily be calculated using Breit’s
method as explained below: For pp electronic configuration, ml 1,0, 1 for each of
the two electrons & ms is either +1/2 or -1/2. Writing ml1 and ml 2 in a horizontal
row and column (written in bold). Similarly, writing the values of ms1 and ms 2 as
shown in following tables. Fill the body of the tables with ml M L and
ms M S .
Table 1
ml 1 1 0 -1
ml 2 1 2 1 0
0 1 0 1
-1 0 -1 -2
L=0 L=1 L=2
308
ms1 +½ -½
ms 2 + ½ 1 0
-½ 0 -1
S=0 S=1
Table 2
Equivalent electrons for a given values of n and l, can have either same ms
or same values of ml . If ms values are same then some combinations of ml will not
be allowed and vice versa.
If ms are same: M L values on the diagonal of the table 1 have same ml and
therefore, not allowed. Likewise, M L values above the diagonal are mirror image of
the values below the diagonal; hence forbidden. What is left are M L 1,0, 1 which
are the magnetic quantum numbers corresponding to L = 1. The combinations of
M L and M S which are left and allowed by the Pauli’s exclusion principle are
ms M S = 1 or -1 (1)
ml M L = 1, 0 -1 (2)
Each of the M L value combines with each of the M S value yielding
M L 1,0, 1 for each of the M S values, that is 1 and -1 all alone has no meaning
unless there is another combination with M S = 0 and M L 1,0, 1 . This deficiency
may be fixed up from the following considerations when same ml is considered.
If ml values are same: Electrons can’t have same values of ms (that is
allowed value of M S is 0 only) but, on the other hand, each of the electrons is free
to have any of the value of ml . Pauli’s principle, therefore allows the following
combinations.
M L 2,1,0, 1, 2 with M S = 0 (3)
M L 1,0, 1 with M S = 0 (4)
M L = 0 with M S = 0 (5)
Relations (1), (2) and (4) lead to L = 1 and S =1 giving the Term 3 P ; (3) and (5)
yield the Terms 1 D and 1 S respectively. Thus two equivalent p electrons yield
Terms (states) 1 S , 3 P , and 1 D .
309
Similar mechanism can be followed for calculating the Terms (states) for
other different number of equivalent p– electron systems.
(iii) Three equivalent p- electrons (Unexcited Nitrogen atom): Possible
number of combinations is 20. The values of M L and M S can be grouped as
M L 1, 0, 1 2, 1, 0, 1, 2 0
1
2 , 2 , 2 , 2
3 1 1 3
M S 2 , 12 12 , 12
The spectral Terms for normal nitrogen atom are
2
L 1, S 12 P3/2,1/2
2
L 2, S 12 D5/2, 3/2
2
L 0, S 32 S3/2
Spectral Terms for excited nitrogen atom are
1
S L 0, S 0 L 1 2
1 1
P
2 P L 1, S 2 S 2
1
D L 2, S 0 L 3,2,1 2
1 1
F , 2 D, 2 P
2 P L 1, S 2 S 2
3
P L 2, S 1 L 2,1,0 4 4 4 2 2 2
1 3 1
D, P , S , D, P , S
2 P L 1, S 2 S 2 , 2
(iv) Four equivalent p electrons: In all possible combination is 6C 4 15 . With
the same reasons, the final spectral Terms are 1 S 0 , 3 P0,1,2 and 1 D2 , which is the
same as due to two p – electrons.
(v) Two equivalent d- electrons: The possible values of ml and ms for one d-
electron are
ms ½ ½ ½ ½ ½ -½ -½ -½ -½ -½
ml 2 1 0 -1 -2 2 1 0 -1 -2
a b c d e f g h i j
Totally, in all there are 10 states and the possible combinations are 10C 2 45 .
Adding the values of ml and ms to these combinations, we get 1 S , 3 P , 1 D, 3 F and 1G
310
15.5.2 jj- Coupling:
Consider the case of three equivalent p- electrons in jj- coupling. The
possible values of quantum number m j are listed below:
j 3/2 3/2 3/2 3/2 ½ -½
mj 3/2 ½ -½ -3/2 ½ -½
a b c d e f
Out of these six states, we can take three at a time with no two of same
kind. The same combinations are obtained as in the case of LS- coupling.
j1 3 / 2, j2 3 / 2, j3 3 / 2 m j 3 / 2,1/ 2, 1/ 2, 3 / 2
j1 3 / 2, j2 3 / 2, j3 1 / 2 m j 1/ 2, 1 / 2
5 / 2,3 / 2,1 / 2, 1/ 2, 3 / 2, 5 / 2
3 / 2,1/ 2, 1/ 2, 3 / 2
j1 3 / 2, j2 1/ 2, j3 1 / 2 m j 3 / 2,1/ 2, 1/ 2, 3 / 2
These 20 terms correspond to five Terms: (3 / 2,3 / 2,3 / 2) 3/2 , (3 / 2,1/ 2,1/ 2)1/2 ,
(3 / 2,3 / 2,1 / 2) 5/2 , (3 / 2,3 / 2,1 / 2) 3/2 and (3 / 2,1/ 2,1/ 2)1/2 .
15.6
15.6Hund’s
Hund’sRule
Rule
This rule is applicable only to LS coupling. In LS coupling, the effect of
spin-spin interaction is usually larger compared to the electrostatic repulsion. It is
found that largest S has lowest energy because the repulsion is taken inversely
proportional to the distance between them. Further the electrostatic energy will be
minimum, if the valence electrons are very far from each other. Therefore, the
electrons of the lowest energy level’s will be then arranged symmetrically around
the nucleus. This symmetric configuration rotates like a rigid body, making thereby
individual electrons to rotate in same direction which finally makes maximum
possible value of L. Thus, the largest L value lies in the lowest energy level. These
results are known as Hund’s rules.
In multi-electron atoms, the energy states with maximum total spin are
more bound as evident by their energy. It is because, no spatial orbital ml of a
given sub shell (l value) will have two electrons unless all others have one electron
each. For example, a p 4 sub shell has occupancy of its electrons as
311
rather than or . It has been shown, that with symmetric spin
eigen function, the electrons are far apart resulting in less screening of the nuclear
charge by the inner electrons. This result in more binding and therefore, lowering
of the states of large more total spin.
Hund’s rules may be restated as follows:
(i) For a given electron configuration, the Term with maximum multiplicity (2S+1)
are lowest.
(ii) Among the Terms with same multiplicity, Terms having largest orbital angular
momentum L lie lowest on energy scale.
The rule holds good for the case of electron configuration involving normal
state (example- nitrogen, carbon, scandium etc.).
15.7Lande’s
15.7 Lande’sInterval
IntervalRule
Rule
The rule determines the separation of fine structure line in LS- coupling.
LS-coupling has the characteristics that the separation between the triplets and the
singlets is large compared to the separation between the multiplet fine structure
which, in turn, follows Lande' interval rule. These characteristics help recognize
the coupling.
As, it is known that fine structure of a level for a given value of L and S is
due to spin-orbit interaction and thus the change in the energy is calculated with
the help of perturbation theory. The change in the energy value is given by
E A2 J ( J 1) L ( L 1) S ( S 1) , (6)
where A is constant.
Thus, the energy values corresponding to the fixed L and S values are given by
E J E0 E
(7)
E0 A2 J ( J 1) L( L 1) S ( S 1)
E J 1 A2 ( J 1)( J 2) L( L 1) S ( S 1) (8)
Thus, the separation between two consecutive levels of fine structure levels is
E J 1 E J E( J 1) J A( J 1) , i.e. proportional to (J+1). In other words,
separation is proportional to the larger J value. Consequently, for a triplet, one may
writes
E( J 2)( J 1) ( J 2)
312
E( J 1) J ( J 1)
E( J 2)( J 1) E( J 1) J ( J 2) ( J 1)
That is ratio of the two consecutive separations is equal to the ratio of the larger J
values. This is known as Lande' interval rule. Therefore, for 3 P0,1,2 ; 3 D1,2,3 and
3
F2,3,4 are in the ratio of 1:2 ; 2:3 and 3:4 respectively.
15.8
15.8Normal
Normaland
andInverted
InvertedTerms
Terms
When fine structure levels are arranged in upward direction in the increasing order
of J value such that the level with smallest J values lie lowest, knows as normal
Terms whereas, the inverted Terms is defined for those when the energy levels of
fine structure are arranged in upward direction with the decreasing order of J value
such that level with largest J value lies lowest. From experimental evidences, it has
also been noticed that normal Terms appear when the electronic configuration of
the concerned element has less than half filled subshell of electrons, while if the
subshell are more than half filled, then inverted Terms appear.
For example, the ground 3 P term of carbon, formed from two equivalent p
electrons, forms a normal multiplet and the ground state 3 P0 . On the other hand,
the ground 3 P term of oxygen, formed from four equivalent p electrons, forms an
inverted multiplet and the ground state is 3 P2 . For atoms having a ground
configuration with an exactly half filled orbital, the ground term is always an S
term, for which the only one state (ground state) arise. For example, the ground
state of chromium is 7 S ,because the quantum numbers l = 0 and S = 3, and J can
take only value 3, and the ground state is 7 S3 .
Further, the fine structure of spectrum of an element also generated due to
the interaction, namely, spin –orbit interaction. Thus, it is possible that order of
energy levels may also governed by spin-orbit interaction energy. Now when the
interaction energy results negative, the Terms are inverted and for positive energy
it turns to the normal Terms.
15.9
15.9Order
OrderofofFine
FineStructure
StructureMultiplets
Multiplets
15.9.1 LS Coupling:
The effects of various terms, like interaction energy due to spin-orbit, spin-spin,
313
orbit –orbit as well as due to electron spin - nuclear spin and nuclear spin – orbital
motion and also electrostatic energy of electrons in attraction and repulsion, splits
up the unperturbed energy levels into many levels and the resultant of those, of
course, lie in a order obeying the Pauli’s principle, Hund’s rule and Lande’s
interval rule.
a. In LS coupling, spin-spin correlation is most dominating factor and because
of it unperturbed energy levels split up into a large number of well spaced levels.
The number is equal to the possible values of S. While calculating the possible S
values, in accordance with the Pauli’s principle, the split levels lie in an order of
decreasing S such that the level with the largest value of S, lies lowest.
b. The second dominating factor is electrostatic effect, which further
influences and splits up each of the above levels. The number of levels is equal to
the possible values of L, which can be formed from the individual angular
momenta of a given number of valence electrons following the Pauli’s principle.
These levels lie in order of decreasing L for a given value of S such that the level
with largest L value lies lowest.
c. The next effective term is spin-orbit interaction. This interaction splits the
level into (2S+1) or (2L+1) levels, whichever is smaller. Here the level with lowest
value of J lies lowest and others in increasing order of J value.
15.9.2 jj- Coupling:
a. In this coupling, spin-orbit interaction is the most dominating factor and it
splits up the unperturbed level into a number of well separated levels. The level
with smaller j value will lie deepest as it has lowest energy.
b. Next effective factors are electrostatic energy and spin-spin interaction,
which contribute in splitting up each of the above levels into a large number of
levels characterized by different values of J. The level with lowest value of J lies
lowest, again in accordance with the Pauli’s principle.
15.10
15.10Selection
SelectionRules
Rules
In order to have complete understanding about the exact nature of the
transitions, it is required to know the rules, namely, Selection Rules which govern
the allowed changes in various quantum numbers when an atom jumps from one
state to other. The selection rules for complicated atom are almost same as for the
314
two electron system. Other selection rules can also be obtained using the symmetry
properties of the states and of the interaction dipole. A detailed analysis leads to
the following selection rules.
15.10.1 Selection Rules for LS- Coupling
The selection rules, when LS coupling is pertinent are similar to those for
one-electron systems. Although, the selection rules for one electron atoms are
based on mathematics of dipole moment, the selection rules for many electrons are
based on both mathematics and experimental proof. In LS coupling ,the main
quantum numbers are L, S, M L an M S . Since the spin does not exist in perturbing
Hamiltonian so one have the selection rule S 0 . As for the case of Hydrogen
atom, the parity must change. The parity is given by the value of l (odd or even) of
jumping electron must change by unity, i.e. ( li ) 1 , where ( li ) is the
change in the sum of individual angular momentum quantum numbers for the
electrons. For total orbital angular momentum, in addition to the selection rule
L 1 . As a whole, for an atom the selection rules for other quantum numbers
are: L 0, 1 ; J 0, 1 but transitions j 0 0 is not allowed. M j 0, 1
but M j 0 0 is not allowed when J 0 .
15.10.2 Selection Rules for jj- Coupling
The selection rules when jj- coupling pertains may be deduced from general
angular momentum. Although L and S are no longer treated as good quantum
number but J, M j and individual j are good. In most common type of spectra,
transitions between the levels take place only when one electron makes the jump at
a time. The orbital quantum number of jumping electron must change by unity, i.e.
L 1 . Thus, the inner quantum number of jumping electron must change by
unity or by 0, i.e. j 0, 1 , but for all other electrons must not change, i.e. j 0
. As a whole, the other quantum numbers changes as: J 0, 1 ; j 0 0 is not
allowed. M j 0, 1 but M j 0 0 is not allowed when J 0 .
15.11
15.11Illustrative
IllustrativeExamples
Examples
Example 1: Find the values of s, L and J for the representation of electron states:
1
S 0 , 3 P2 , 2 D3/2 and 5 F5 .
Sol. (i) 1 S 0 : 2s+1=1 s=0; S L=0; J = 0.
315
(ii) 3 P2 : 2s+1=3 s=1; P L=1; J = 2
(iii) 2 D3/2 : 2s+1=2 s=1/2; D L=2; 3/2 J = 3/2
(iv) 5 F5 : 2s+1=5 s=2; F L=3; 5 J = 5
Example 2: Find Term values (states) for the electronic configuration pd of an
atom under LS- and jj- coupling schemes.
Sol. Given that l1 1, l2 2 an s1 s2 1/ 2 .
(i) Under LS- coupling scheme
L ( l1 l2 ),( l1 l2 1),(l1 l2 2).......... l1 l 2 3,2,1 , which is F, D, and P
states.
S ( s1 s2 ),( s1 s2 1),( s1 s2 2).......... s1 s2 1,0 , i.e. (2S+1) = 3, 1.
Thus corresponding Terms are: 3 F , 3 D, 3 P (triplets) and 1 F , 1 D, 1 P
(singlets). Therefore, the J values for each of the triplet and singlet states as given
by J ( L s),( L S 1), ........ L S
For 3 F and J 4,3,2 ; Terms are 3 F4,3,2 ;
For 3 D and J 3,2,1 ; Terms are 3 D3,2,1 .
For 3 P and J 2, 1, 0 ; Terms are 3 P2,1,0 ;
For 1 F and J = 3, Term is 1 F3 ;
For 1 D and J = 2, Term is 1 D2 ;
For 1 P and J = 1, Term is 1 P1 .
(ii) Under jj- coupling scheme
j1 ( l1 s1 ),(l1 s1 1),.......... l1 s1 3 / 2,1/ 2
j2 ( l2 s2 ),( l2 s2 1),.......... l 2 s2 5 / 2,3 / 2
Each of j1 value combines with each of the j2 value give four Terms, represented
by (3 / 2, 5 / 2), (3 / 2, 3 / 2), (1 / 2, 5 / 2) , and (1 / 2, 3 / 2) . J values for each of the
combinations is given by
J ( j1 j2 ),( j1 j2 1), ( j1 j2 2).......... j1 j2 .
316
For (3 / 2, 5 / 2) ; J = 4, 3, 2, 1; Terms are (3 / 2, 5 / 2) 4,3,2,1 .
For (3 / 2, 3 / 2) ; J = 3, 2, 1, 0; Terms are (3 / 2, 3 / 2)3,2,1,0 .
For (1 / 2, 5 / 2) ; J = 3, 2; Terms are (1 / 2, 5 / 2) 3,2 .
For (1 / 2, 3 / 2) ; J = 2, 1; Terms are (1 / 2, 3 / 2) 2,1 .
Example 3: A two electron atom in an excited state has one electron in d- state and
one in f- state, coupled according to LS scheme. Show that there are 20 possible
Terms (states), which are either singlet or triplets. Write them.
Sol. Given l1 2 , l2 3 and s1 s2 1/ 2 .
From these, we have L = 5, 4, 3, 2, 1 corresponding to H, G, F, D and P states and
S = 1, 0. Under LS- coupling scheme, we get following J values
L S J States J=L S States
5 1 6, 5, 4 3 H 6,5,4 5 0 1H 5
4 1 5, 4, 3 3
G5,4,3 4 0 1G 4
3 1 4, 3, 2 3
F4,3,2 3 0 1 F3
1
2 1 3, 2, 1 3
D3,2,1 2 0 D2
1
1 1 2, 1, 0 3
P2,1,0 1 0 P1
2 s 1
Example 4: Write the complete ground state term in LS notation, i.e. LJ , for
the elements in the first row of the periodic table, i.e. Li through Ne.
Sol.
Li: 1s 2 2 s ; L 0; S 1/ 2; J 1/ 2 2 S1/2
Be: 1s 2 2 s 2 ; L 0; S 0; J 0 1 S 0
B: 1s 2 2 s 2 2 p ; L 1; S 1/ 2; J 3 / 2,1/ 2 2 P1/2
C: 1s 2 2 s 2 2 p 2 ; the possible terms are 3 P , 1 D , 1 S and by Hund's rule, the lowest-
lying must be the triplet, since the p- shell is less than half full, i.e. 3 P0 .
N: 1s 2 2 s 2 2 p 3 ; the possible terms are 4 S , 2 D , 2 P . The quartet will lie lowest.
Since L 0 , because l = 0 and thus there is only one value of J for this state,
i.e. 4 S3/2 .
317
O: 1s 2 2 s 2 2 p 4 ; the possible terms are 3 P , 1 D , 1 S (same as carbon), so by Hund's
rule, Since the p-shell is more than half full and the highest J lies lowest, i.e.
3
P2
F: 1s 2 2 s 2 2 p 5 ; Possible states are the same as boron, except the highest J will lie
2
lowest, i.e. P3/ 2
Ne: 1s 2 2 s 2 2 p 6 ; Closed shell configuration so the ground state is the same as
helium, 1 S 0 .
Example 5: (a)Write all terms for the electron configuration npn ' p in both the LS-
and jj-coupling notation.
(b) Make a diagram similar to Figure 3 for the jj-coupling states showing the
effects of spin-orbit interaction and exchange and electrostatic repulsion. Put all
terms in proper order.
Sol.(a) LS- coupling: Given S 0,1; L 0,1,2
Possible states: 3 D3,2,1 ; 3 P2,1,0 ; 3S1 ; 1 D2 ; 1P1 ; 1S 0
3 1 3 1
jj- coupling: j1 , ; j2 , ; J 3,2,1,0
2 2 2 2
Possible states:
1 1 ; 1 1 ; 1 3 ; 1 3 ; 3 1 ; 3 1 ; 3 3 ; 3 3 ; 3 3 ; 3 3
2 2 0 2 2 1 2 2 2 2 2 1 2 2 2 2 2 1 2 2 3 2 2 2 2 2 1 2 2 0
(b)
15.12Self
15.12 SelfLearning
LearningExercise
Exercise
Q.1 What states arise from the terms (a) 3 S , (b) 4 P , (c) 5 D and (d) 2 F ?
318
Q.2 What terms arise from the excited configurations (a) 1s 2 2 s 2 2 p1 4 f 1 , and (b)
1s 2 2 s 2 3d 1 4 f 2 of carbon atom?
Q.3 Compare the terms arise from two non-equivalent p electrons with those that
arise from two equivalent p electrons.
15.13
15.13Summary
Summary
Starting with the spectra of two valence electrons as case study and
extended the idea for many electron systems for understanding the complicated
(complex) spectra. Proceeding in sequence, we have studied well the Russell-
Saunder’s (LS) and jj- coupling and derived the spectral terms, namely, S, P, D,
F…. for the new energy levels generated after the splitting of original levels, which
occur after the various types of possible interactions. Effects of LS and jj- coupling
have been studied for equivalent and non-equivalent electrons system. Further, the
Selection rules have been followed for possible interactions and thus spectral
terms. A brief about the rules, namely, Hund’s rule, Lande’s Interval rule have
been outlined for complete explanation of experimental multiplets of fine structure.
Substantive examples have also been worked out for better understanding.
15.14Glossary
15.14 Glossary
Multiplet: (i) A spectral line having more than one component, representing slight
variations in the energy states characteristic of an atom. (ii) Any group of
subatomic particles that are similar in most properties, but have different electric
charges, such as the nucleons, which form a doublet, or the pions, which form a
triplet.
Spectral Term: It is an abbreviated description of the angular momentum quantum
numbers in multi electron system.
Fine Structure: The presence of groups of closely spaced lines in spectra
corresponding to slightly different energy levels
Hyperfine Structure: It is the different effects leading to small shifts and splitting
in the energy levels of atoms, molecules and ions.
Coupling: It is an indirect interaction between two nuclear spins which arises from
hyperfine interactions between the nuclei and local electrons
319
Precession: A change in the orientation of the rotational axis of a rotating body or
the slow movement of the axis of a spinning body around another axis due to a
torque acting to change the direction of the first axis.
15.15
15.15Exercise
Exercise
Q.1 Find the LS terms that arise from the following configurations:
(a) nsnp (b) npnd (c) ( np) 2 ns
Q.2 Write all terms for the electron configuration np 2 in both LS- and jj-coupling
notation. (b) Make a diagram showing the transition from LS- to jj-coupling.
Put all terms in proper order.
Q.3 Deduce the spectral Terms arising from the configuration 3pnd in the case of
jj- coupling. Which of the terms is likely to be the lowest in energy?
Q.4 Calculate all spectral terms for three equivalent p- electrons in unexcited
nitrogen atom.
References
Referencesand
andSuggested
SuggestedReadings
Readings
12. Bransden and Joachain, Physics of Atoms and Molecules, (2009), Benjamin
Cummings.
13. Raj Kumar, Atomic and Molecular Spectra: Laser , Kedarnath Ram Nath Pub.
14. SL Gupta, V Kumar, RC Sharma, Elements of Spectroscopy, Pragati
Prakashan.
15. Rajam J. B., Atomic Physics (2007), S Chand & Co, New Delhi.
16. S.N. Thakur and D.K. Rai, Atom, Laser and Spectroscopy, PHI Learning Pvt.
Ltd.
17. Fewkes J.H. and Yarwood J. Atomic Physics Vol II (1991) ,Oxford University
Press.
18. Rita Kakkar, Atomic and molecular spectroscopy, Cambridge University Press
(2015).
19. http://users.aber.ac.uk/ruw/teach/327/lsjj.php
20. http://www.chem.uwimona.edu.jm/courses/RScoupling.html
21. http://physics.nist.gov/Pubs/AtSpec/
22. http://nptel.ac.in/courses/
320
UNIT-16
Spectra of Alkali and
Alkaline Earth Elements
Structure of the Unit
16.0 Objectives
16.1 The spinning electron
16.2 Intensity ratio for doublets
16.3 Illustrative Examples
16.4 Self Learning Exercise-I
16.5 Vector model for Two valence electron atom
16.6 Interaction energy in LS and JJ coupling
16.7 Illustrative Examples
16.8 Self Learning Exercise-II
16.9 Summary
16.10 Glossary
16.11 Answers to Self Learning Exercises
16.12 Exercise
16.13 Answers to Exercise
References and Suggested Readings
16.0
16.0 Objectives
Objectives
In this chapter, we will concentrate on the fine structure of the one electron atoms.
The cause of this fine structure is the interaction between the orbital angular
momentum and the spin angular momentum. The chapter will also review the
origin for this interaction and the effect of the coupling between orbital and spin on
the spectral lines.
321
16.1
16.1The
TheSpinning
SpinningElectron
Electron
In spectroscopy, Fine structure is the splitting of the main spectral lines of
an atom into two or more components. Each component represents a slightly
different wavelength. In alkali metals such as sodium and potassium, there are two
components of fine structure, which are called doublets. For e.g. the yellow D-line
of Sodium consists two close lines, the wavelengths of which are 5890 and
5896 Ao.
In the spectral lines of different series, the nature of fine structure is different.
Experimental findings reveal that emission spectra of the alkali atoms can be
analyzed into so called four chief series with the peculiarities as given below.
1. All the lines of sharp series consist of doublets; separation between the doublet
components remain constant as far as the series extends.
2. Similarly, each line of the principal series is also a doublets, however the
separation between the doublet components decreases rapidly as the series
extends to higher members.
3. Third series initially consists of triplets (three components) followed by
apparent doublets; separation between the outer components remain constant as
far as the series extends. Series is termed as diffuse series.
4. Fourth series, termed as Fundamental series, lies in far infra-red region and
consists of very close lying doublets.
In general, for lighter atoms the fine structure splitting of spectra lines is small
which increases with the increase in the atomic number.
Explanation of fine structure:
Fine structure is produced when an atom emits light in making the transition from
one energy state to another. The split lines, which are called the fine structure of
the main lines, arise from the interaction of the orbital motion of an electron with
the quantum mechanical “spin” of that electron. An electron can be thought of as
an electrically charged spinning top, and hence it behaves as a tiny bar magnet.
The spinning electron interacts with the magnetic field produced by the electron’s
rotation about the atomic nucleus to generate the fine structure. Due to the spin-
orbit interaction, the orbital angular momentum l is coupled to the spin angular
322
momentum s. The quantum number j, which is also known as ‘inner quantum
number’ can take values between l+s to l-s. As s can take only ½ value, each
energy level gets split into two, one corresponding to j=l+1/2 and another j=l-1/2.
The complete notation of the levels will be as given below:
Level l s Multiplicity j(=l±s) Full
(2s+1) notation
2
S 0 1/2 2 1/2 S1/2
2
P 1 1/2 2 3/2, 1/2 P3/2, 2P1/2
2
D 2 1/2 2 5/2, 3/2 D5/2, 2D3/2
2
F 3 1/2 2 7/2, 5/2 F7/2, 2F5/2
The component corresponding to smaller j value is stable and hence lies deeper in
the doublet. This is due to the fact that, in the stable state, the spin magnetic
moment µs of the electron has the same direction of the magnetic field B, which is
produced by the orbiting electrons. This is also the same direction as that of the
orbital angular momentum l. Since µs and spin angular momentum s has opposite
direction, l is also opposite to s. Hence in the more stable state, j takes the value l-s.
Calculation of Level splitting due to Spin-Orbit interaction:
The expression for spin-orbit interaction energy can be written as [Ref: Unit 14]
( )
∆ , = [ ( + 1) − ( + 1) − ( + 1)]
(1)
For l=0, the spin-orbit interaction energy ∆ , = 0. For other values of l, ∆ ,
assumes two values: one positive and another negative.
According to Hartree theory, in an alkali atom, the optical electron in a shell n is
considered to be moving in a potential field
1
( )=−
4
where is a constant and equals to ( ). ( )is given by
323
( )→ →0
( )→1 →∞
is the effective nuclear charge for shell n.
Substituting the expression for the potential in the expression of spin-orbit
interaction energy and after solving, eq. (i) can be written as:
ℎ 1
∆ , = [ ( + 1) − ( + 1) − ( + 1)]
4 (16 )
where the average value of is given as,
1
=
1
+ ( + 1)
2
=4 is the radius of the smallest Bohr orbit of the Hydrogen
atom. Using these, the final expression for the energy reduces to
ℎ
∆ , = [ ( + 1) − ( + 1) − ( + 1)]
1
2 + ( + 1)
2
where, = is known as Rydberg constant, and = = is
known as fine structure constant and is dimensionless.
The term shift due to spin-orbit interaction is
∆ ,
∆ , =−
ℎ
= [ ( + 1) − ( + 1) − ( + 1)]
1
2 + ( + 1)
2
Now, for a single electron system, =
1
= ±
2
324
Substituting these values of j in the expression for energy, the term shift
corresponding to = + and = − can be given as,
∆ , =
1
2 + ( + 1)
2
∆ , = ( + 1)
1
2 + ( + 1)
2
Thus due to the spin-orbit interaction, each level gets split into two levels
corresponding to two values of j. The separation between these two levels is
∆ =∆ , −∆ ,
Substituting the values of and = we get,
( − )
∆ = 5.84
( + 1)
This formula gives the doublet separation, which is remarkably good in agreement
with experimental variation. This shows that (i) The level splitting for an alkali
atom increases with the increase in atomic number (ii) For the same l, the level
spitting decreases with increasing n and (iii) For the same n, it decreases with
increasing n.
16.2
16.2Intensity
IntensityRatio
Ratiofor
forDoublets
Doublets
The line intensities in doublet spectra show that:
(1) The strongest line in any doublet arises from transition in which j and l
change in one way.
(2) When there is more than one such line, the line involving the larger j value is
strongest.
For eg. in the principle series doublet shown above, the line arising from the
transition 2P3/2-2S1/2 is stronger than 2P1/2-2S1/2. The reason is that in the first
transition, j changes by 1 and l changes by -1 while in the second transition j
changes by 0 and l changes by -1.
325
3 2P3/2
3 2P
3 2P1/2
3 2S 3 2S1/2
D1 D2
ν
The intensity ratio is then defined as,
3
2 +1 4
= 2 = =2∶1
1
2 +1 2
2
The same holds for the members of principal series.
Let us consider another example. The diffuse series compound doublet:
3 2D5/2
3 2D
3 2D3/2
a b c
3 2P 3 2P3/2
3 2P1/2
b
c
a
The lines a and c start from 2D3/2 while the line b starts from 2D5/2. Therefore,
= = = (i)
326
Line c ends on 2P1/2 while lines a and b end on 2P3/2. Thus
= = = (ii)
Solving (i) and (ii) we get,
1 5
∶ ∶ = ∶1∶
9 9
∶ ∶ =1∶9∶5
If the line a is not resolved from line b ,then we shall see two lines having intensity
ratio
(1 + 9) ∶ 5 = 2 ∶ 1
16.3Illustrative
16.3 IllustrativeExamples
Examples
Example 1: The first member of the principle series of sodium has a wavelength
of 5893 A0. First excited s state of sodium lies 3.18 eV above the ground state.
Find the length of the first member of the sharp series. Given e=1.60×10-19C,
c=3×108 ms-1
Sol. The first member of the principal series corresponds to the transition 3p-3s.
The energy corresponding to this transition (wavelength =5893 A0 ) is
E1(3p-3s)=hc/λ
= 3.375 × 10-19J
= 2.11 eV
The energy corresponding to the first excited state 4s of Sodium relative to the
ground state 3s is:
E2(4s-3s)=3.18 eV
The first member of sharp series corresponds to the transition from 4s-3p. The
energy corresponding to this transition is:
E(4s-3p)= E2(4s-3s)- E1(3p-3s)
=3.18 eV-2.11 eV
=1.07 eV
327
Corresponding wavelength is
λ=hc/E= 11618 A0
16.4
16.4 Self
SelfLearning
LearningExercise-I
Exercise-I
Q.1 Write down the normal electronic configuration of Helium and lithium
atoms. Determine the states to which these configurations give rise.
Q.2 Calculate the wavelength of the line corresponding to 2p-2s transition in
Lithium. The 2p level lies 1.85 eV higher than the 2s level.
Q.3 Define intensity ratio of doublets.
16.5 Vector
16.5 VectorModel
Modelfor
forTwo-Valence
Two-ValenceElectron
ElectronAtom
Atom
Alkaline Earth atoms like Beryllium, Magnesium, Zinc, Cadmium, Mercury,
Calcium and others in group IIA and IIB of the periodic table contain two valence
electrons and give rise to series of singlet and triplet spectral lines. The analysis of
these spectra by Russell and Saunders in 1925 was an important development in
the theoretical understanding of atomic spectroscopy. The current topic deals with
the observed spectral features and finally the vector model description of the atom
that emerged out of these studies.
In the vector atom mode, the orbital angular momentum of each electron is
represented by l, and the spin angular momentum by s. Under varying
circumstances, the vector l and s, combine to form resultant vectors in terms of
which the observed properties can be explained.
In alkaline earth metals, the vector atom model consists of vectors l1 ,l2 ,s1 ,s2 and
their resultant J. The formation of J can be understood in terms of L-S and j-j
coupling.
L-S Coupling:
This coupling occurs in the lighter atoms. In the vector model of L-S coupling, the
angular momentum vector of individual electrons l1 , l2 precess rapidly. The
corresponding quantum number L can then take the values from |l1- l2| to |l1+ l2|.
The various terms according the values of L=0,1,2… are termed as S,P,D,…
Similarly the spin angular momentums s1 ,s2 combines to form a resultant angular
momentum S. It can take values between |s1- s2| to |s1+s2|. Since s1 ,s2 can have
328
values ½, S=0, 1. The multiplicity 2S+1 has values 1 and 3. Thus the two valence
electron system leads to singlet and triplet states.
As a result of spin-orbit interaction, L and S couples with each other to form the
total angular momentum vector J. The value of J is given by, J=L+S. The quantum
number J thus takes values from |L-S | to |L+S |.
This shows that the spin orbit interaction breaks each level which is characterized
by an L value in a number of fine structure characterized by a J-value. The
collection of fine-structure levels is known as a ‘multiplet’.
Fig: L-S coupling
Eg. Calcium atom (Ca)
The ground state configuration of Ca is 1s2 2s2 2p6 3s2 3p6 4s2
For the two optically active electrons we have, l1=0, l2=0 and s1=1/2, s2=1/2
Thus, L=0 (S-term)
S=0, 1
J=0, 1
The terms are 1S0 and 3S1. Since the two valence electrons in 4s2 are equivalent, the
329
term 3S1 is excluded by Pauli’s principle. Hence the normal atom gives rise to a
singlet-S terms i.e. 1S0 only.
j-j Coupling:
In light atoms, the interactions between the orbital angular momenta of individual
electrons is stronger than the spin-orbit coupling between the spin and orbital
angular momenta. These cases are described by "L-S coupling". However, for
heavier elements with larger nuclear charge, the spin-orbit interactions become as
strong as the interactions between individual spins or orbital angular momenta. In
those cases the spin and orbital angular momenta of individual electrons tend to
couple to form individual electron angular momenta.
In j-j coupling, the orbital angular momentum l, and spin s, of each electron are
first coupled to form a total angular momentum j, for that electron. These single-
electron total angular momenta are then combined into a total angular momentum
J, for the group of electrons. This is in contrast to LS coupling, where the total
orbital angular momentum L and total spin S, of the system are calculated first and
then combined to the total angular momentum J, of the whole system.
Fig: j-j coupling
16.6
16.6 Interaction
InteractionEnergy
EnergyininLS
LSand
andJJJJCoupling
Coupling
Due to the spin orbit interaction, the atomic term consists of different energies.
330
Each of them is slightly different and corresponds to different J values. Thus the
multiplet splitting increases rapidly with increase in atomic number Z.
As we already know, the interaction energy for a single electron atom is given by,
−∆ , = [ ( + 1) − ( + 1) − ( + 1)]
1
2 + ( + 1)
2
∗ ∗
− − ∗
=
2
∗ ∗
where, = , = ( + 1), = ( + 1),
( )
∗
= ( + 1)
In case of two optical electrons, there are four angular momentum, i.e. l1*, l2*, s1*,
s2*. The possible interactions are,
(1) l1* with l2*
(2) s1* with s2*
(3) l1* with s1*
(4) l2* with s2*
(5) l1* with s2*
(6) l2* with s1*
The interactions (1) and (2) dominate over (3) and (4). Interactions (5) and (6) are
negligible.
Using equation (1), the energies corresponding to interactions (1), (2), (3), and (4)
can be written as,
∗ ∗
∆ = cos ( ∗ , ∗ )
∗ ∗
∆ = cos ( ∗ , ∗ )
∗ ∗
∆ = cos ( ∗ , ∗ )
∗ ∗
∆ = cos ( ∗ , ∗ )
In LS coupling, l1* and l2* precess rapidly around their resultant L*. Using Cosine
law, we can write:
331
∗ ∗ ∗ ∗
∗ = + +2 cos ( ∗ , ∗ )
1
∆ = ( ∗− ∗ − ∗ )
2
Similarly s1 and s2 precess rapidly around their resultant S*.
* *
∗ ∗ ∗ ∗
∗ = + +2 cos ( ∗ , ∗
)
This gives,
1
∆ = ( ∗ − ∗ − ∗ )
2
To calculate the interaction energy between l1* and s1* and between l2* and s2* the
average values of cosine must be calculated. The average values are given by,
cos( ∗ , ∗)
= cos ( ∗ , ∗
)cos ( ∗ , ∗
)cos ( ∗ , ∗
)
cos( ∗ , ∗ ) = cos ( ∗ , ∗ )cos ( ∗ , ∗ )cos ( ∗ , ∗ )
Substituting the average values of the cosines in equation (ii), we get
∆ + ∆ = [ ∗ ∗ cos( ∗ , ∗ ) cos( ∗ , ∗ )
∗ ∗
+ cos( ∗ , ∗ ) cos( ∗ , ∗ )] cos( ∗ , ∗ )
Using cosine law and after simplification, we get
∗
+ ∗ − ∗ ∗ + ∗ − ∗
=
2 ∗ 2 ∗
∗
+ ∗ − ∗ ∗ + ∗ − ∗ ∗
− ∗
− ∗
+
2 ∗ 2 ∗ 2
This after further simplification can be written as,
1
∆ +∆ = ( ∗ − ∗ − ∗ )
2
where = +
∗ ∗ ∗ ∗ ∗ ∗
and, = ∗ ∗
∗
+ ∗ − ∗ ∗ + ∗ − ∗
=
2 ∗ 2 ∗
We can now write any fine-structure term by the formula,
332
= −∆ −∆ −∆ −∆
where, T0 is a hypothetical term which accounts for the center of gravity of entire
electron configuration.
16.7
16.7 Illustrative
IllustrativeExamples
Examples
Example 2. Consider a carbon atom whose electrons are in the configuration (1s)2
(2s)2 2p 3p. List all expected terms on the basis of the LS (Russell-Sanders)
coupling scheme.
Sol. (1s)2 couples to L=0, S=0. (Pauli Exclusion Principle)
(2s)2 couples to L=0, S=0. (Pauli Exclusion Principle)
The 2p and 3p electrons both have l=1, s=1/2. This can lead to L=2,1,0, S=0,1.
We therefore can form the following terms:
1 3 1 3 1 3
D2, D123, P1, P012, S0, S1
Example 3 Scandium has a ground state configuration 1s2 2s2 2p6 3s2 3p6 4s2 3d.
Consider a transition from the ground state 4s2 3d to the excited state 3d 4s 4p.
Assuming LS coupling find L, S, and J values for the terms derived from the 4s2 3d
and 3d 4s 4p configurations.
Write down each term in standard notation.
Sol. LS coupling: L=2; S=1/2
Possible terms: 2D5/2, 2D3/2
16.8
16.8 Self
SelfLearning
LearningExercise-II
Exercise-II
Q.1 The atomic number of Carbon is 6.
(i) State its electronic configuration.
(ii) Calculate the spectroscopic terms for this configuration.
(iii) If one of the 2p electrons gets excited to the M-shell, what other
spectroscopic terms will be possible?
Q.2 Write down the electronic configuration of N+ and deduce the spectral
terms.
Q.3 Obtain the terms for the ground state of neutral oxygen atom.
333
16.9
16.9 Summary
Summary
The closely spaced groups of lines observed in the spectra of the lightest elements,
notably hydrogen and helium. The components of any one such group are
characterized by identical values of the principal quantum number n, but different
values of the azimuthal quantum number l and the angular momentum quantum
number j.
In atoms having several electrons, this fine structure becomes the multiplet
structure resulting from spin-orbit coupling. This gives splitting of the terms and
the spectral lines that are “fine’’ for the lightest elements but that are very large, of
the order of an electronvolt, for the heavy elements.
Careful examination of the spectra of alkali metals show that each member of some
of the series is closed doublets. For example, sodium yellow line, corresponding to
3p-3s transition, is a close doublet with separation of 6A0while potassium (K) has a
doublet separation of 34A0 and so on. Further investigations show that only the S-
terms are singlet, while all the other terms P, D, F etc. are doublets. Such doublet
structure in energy is observed for all the atoms possessing a single valence
electron i.e., in the outer most shell. Usually the doublet spacing is small compared
to the term difference (for Na the main D line is centered at 5893A0; D2= 5890 A0
and D1 = 5896A0) and hence it is called fine structure.
16.10
16.10Glossary
Glossary
Ground state: The state of lowest intramolecular energy.
Line width: The width of a spectral line.
Quantum Number : According to quantum mechanics, the distribution of
electrons labels the state of the electron and specifies the value of a property in an
atom.
n- Principal Quantum Number (shell number): The average distance of the
electron from the nucleus in a particular orbital; can have integral values of 1, 2, 3,
and so forth.
l- Angular Momentum Quantum Number: (subshell of one shell): Its value
reflects the orbital shape; it correlates with n; (l=n-1); which reveals 0 for the s, 1
for p, 2 for d, 3 for f.
334
16.11
16.11Answers
AnswerstotoSelf
SelfLearning
LearningExercises
Exercises
Answers to Self Learning Exercise-I
Ans.1: 2He: 1s2, 1S0
3
Li: 1s2, 2s, 2S1/2
Ans.2: 6719 A0
Ans.3: See section 16.2
Answers to Self Learning Exercise-II
Ans.1: (i) 1s2 2s2 2p2 (ii) 1S, 1D, 3P (iii) 2p 3s: 1P 3P
2p 3p: 1S 1P 1D; 3S 3P 3D
2p 3d: 1P 1D 1F; 3P 3D 3F
Ans.2: 1s2 2s2 2p2; 1S01D23P0,1,2
Ans.3: 1S01D23P03P13P2
16.12
16.12Exercise
Exercise
Q.1 What is the significance of quantum number J ?
Q.2 What J is equal to ?
Q.3 What are the possible values of J ?
Q.4 Distinguish between LS (RS) and jj coupling.
16.13
16.13Answers
AnswerstotoExercise
Exercise
Ans.1: In lighter elements spin-orbit coupling is small, while in heavier
elements, it is large or appreciable. Hence, the new quantum number J
becomes important. This quantum number gives the total angular
momentum.
Ans.2: j=l+s
Ans.3: J = L+S, L+S-1,......, L-S
Ans.4: Russell – Saunders is known as RS coupling. According to this scheme,
electronic repulsions are stronger than spin -orbit coupling. In lighter
elements, spin -orbit coupling is small and hence RS coupling is valid.
335
Specifically, it is valid for first transition series (3d elements). But in the
case of heavier elements, spin- orbit coupling is more
powerful than electron repulsions. Hence, jj coupling is more
important than RS coupling. In RS coupling, configuration is split
into terms by electron repulsion and these are further split into states
by spin -orbit coupling. But jj coupling is exactly the reverse of RS
coupling. Thus, in jj coupling, configuration is split into levels by spin
-orbit coupling and not terms. These levels are split further by electron
repulsions.
Referencesand
References andSuggested
SuggestedReadings
Readings
1. A. Beiser, Concept of Modern Physics (1987), McGraw Hill Co. Ltd, New
Delhi
2. J. B. Rajam, Atomic Physics (2007), S Chand & Co, New Delhi
3. J.H. Fewkes and J. Yarwood Atomic Physics Vol II (1991) Oxford University
Press
4. B.H. Bransden and C.J. Joachain, Physics of Atoms and Molecules 2nd Ed.
(2009), Pearson Education, New Delhi.
5. C.N. Banwell, and E. Mccash, Fundamentals of Molecular&Spectroscopy.
McGraw-Hill Education (India) Pvt Limited, 1994
6. Atom, Laser And Spectroscopy By S. N. Thakur, D. K. Rai
336
UNIT-17
Zeeman
ZeemanEffect
Effectand
andPaschen
Paschen-Back
-BackEffect
Effect
Structure of the Unit
17.0 Objectives
17.1 Introduction
17.2 Experimental Set-up for studying Zeeman Effect
17.3 Explanation of normal Zeeman Effect
17.4 Zeeman Effect in Hydrogen
17.5 Illustrative Examples
17.6 Self-Learning Exercise-I
17.7 Explanation of Anomalous Zeeman Effect
17.8 Sodium Zeeman Effect
17.9 Paschen-Back Effect
17.10 Transition from Weak to Strong Field
17.11 Zeeman Effect in Some Transitions (examples)
17.12 Illustrative Examples
17.13 Self-Learning Exercise-II
17.14 Summary
17.15 Glossary
17.16 Answers to Self-Learning Exercises
17.17 Exercise
17.18 Answers to Exercise
References and Suggested Readings
17.0
17.0Objectives
Objectives
To describe an atom we have to give a unique set of discrete energy states. When
that atom gets excited through heating or some other way, the atom makes
transitions between these quantized energy states. When atom (electron) comes
back to ground state it emits a photon (light). If we record the emitted photon on a
screen, we get a spectrum which shows the quantized nature of energy levels.
When we apply magnetic field to it, these energy levels can shift from original
337
state. This effect is known as Zeeman Effect.
Dutch physicist Pieter Zeeman studied this effect for splitting of spectral
lines into several components in the presence of a static magnetic field. In 1896,
Zeeman observed that when a sodium source was placed in an external magnetic
field, the yellow D lines were split into several components. Faraday had
performed the same experiment some thirty years earlier, but had failed to observe
an effect because of low resolution of his spectrograph. Splitting of spectral lines
was predicted by Faraday on the basis of classical theory by Lorentz and first
observed by Zeeman. This effect is named after Pieter Zeeman as Zeeman Effect
and he shared 1902 Nobel Prize in Physics with Hendrik Lorentz.
17.1 Introduction
17.1
When we look at a light source with line spectrum, which is placed in an
external magnetic field, the spectral lines emitted by the atoms of the source will
split into a number of polarized components. If we put the magnetic field than the
splitting will be proportional to the strength of applied magnetic field. Due to
Zeeman Effect some degenerate energy levels will split into several non-
degenerate energy levels with different energies and due to this effect we get few
new transitions which can be seen as new spectral lines in the atomic spectrum.
We look at the singlet spectral line right angles to the magnetic field
direction than it will split into three plane-polarized components: un-shifted central
line in which electric vector is vibrating parallel to the magnetic field (called
component) and two other lines equally displaced on both sides with electric vector
vibrating perpendicular to the magnetic field (called components). This effect in
known as ‘normal’ Zeeman Effect and it is called a 'normal triplet'.
ANY
SINGLET SODIUM PRINCIPAL DOUBLET
NO FIELD
MAGNETIC FIELD
PRESENT
σ π σ σ ππ σ σσππσσ
Normal Triplet Anomalous Patterns
Fig 1 Multiplet spectral lines, (i) it shows Normal triplet, (ii) D1 and D2
component of sodium line.
338
If we measure the fine-structure components of a multiplet spectral line, we
get complex Zeeman pattern. For example, due to Zeeman effect D1 and D2
components of sodium yellow doublet split in four and six lines respectively. This
effect is known as ‘anomalous’ Zeeman effect. Zeeman splitting is smaller in
comparison to fine-structure splitting.
17.2
17.2Experimental
ExperimentalSet-up
Set-upfor
forstudying
studyingZeeman
ZeemanEffect
Effect
To make experimental setup for studying Zeeman Effect, we need high
resolving power and large light-gathering power. Schematic diagram of constant-
deviation prism spectrometer arrangement is given in figure 2.
Constant Deviation Prism
T
Lummer-Gehrcke
Collimator Plate
C
Telescope
Micrometer
Fig 2.Schematic diagram of constant-deviation prism spectrometer
arrangement.
Here (in figure 2), T is a neon discharge tube (line source) placed between the
poles of an electromagnet. (If we want to look at another spectrum like cadmium
lamp, sodium etc., then we have to use corresponding lamp)C is positive lens
which is also known as condenser lens. Lens should be adjusted in the position that
the light coming from the capillary part of the tube can be focused on the slit of the
collimator of the spectrometer. A high resolving optical device should be kept
between the collimator and constant deviation prism. In above setup, we kept a
Lummer-Gehreke plate (L-G plate)as a high resolving optical device. A telescope
is fitted with a micrometer eyepiece to measure the light emerging from the prism.
It emerges at the right angles to its initial direction.
For the above setup, we have to follow these steps:
(i) In first step, we keep the electromagnet off. Remove the focusing (condenser)
lens C, L-G plate and micrometer eyepiece. In this state collimator slit will be
fairly wide opened. In telescope, we can see images of pole-pieces and the
neon tube. The pole-piece and the neon tube are so adjusted that the image of
339
the pole-piece appears central in the field of view, and the neon tube is
symmetrical between the pole-pieces.
(ii) Put the focusing lens C in between the electromagnet and slit of the collimator,
such that it’s aperture is fully illuminated. The image of the aperture should
fill the field of view. The micrometer eyepiece should be kept in position and
focused on the crosswire. Now, on looking through it, a bright spectrum of
neon light is seen.
b b
a a
(i) (ii)
Fig 3. View at eyepiece.(i)Before switching on electromagnet.(ii) After
switiching on electromagnet.
(iii) Mount the L-G plate on its stand which is kept in position on the spectrograph.
Look through the eyepiece, each spectral line shows a few orders. We can
adjust the plate in various directions using screws. To get bright and sharp
fringe-system, we have to fairly rotate the screws.
(iv) Recognize the singlet yellow line (λ = 5852 Å) of the spectrum and set the
cross-wire on a few successive orders (fringes). We have to take micrometer
reading.
(v) Now, switch on the electromagnet and adjust the current on the scale where
we can get the magnetic field about 4000 Gauss. Each order will split into
three components: one, which is not displaced from the original line and other
two will be symmetrically displaced. By putting the crosswire on each
(displaced and not displaced line) we can take these reading through
micrometer.
(vi) Change the value of current to get the spectrum on another magnetic field and
340
repeat the process. For example magnetic field is 7000 Gauss and 10k Gauss.
Now, we have to perform the same process for singlet red line (λ = 6266 Å) of
the neon spectrum.
17.3
17.3Explanation
ExplanationofofNormal
NormalZeeman
ZeemanEffect
Effect
All lines due to transition between the singlet (S = 0) states of an atom or
the normal Zeeman Effect can be explained from the classical electron theory. It
can be also explained from the quantum theory with the ignorance of electron spin.
In quantum theory, an atom with electrons more than one possesses an
orbital angular momentum ⃗ with an orbital magnetic moment ⃗. A ratio known as
gyromagnetic ratio (or sometimes magnetogyric ratio; ratio of magnetic moment to
angular momentum of a particle) can be given by
⃗
=
⃗ 2
Here e is the charge of an electron (1.6 × 10 ) and m is the mass of elctron.
Magnetic moment and angular momentum of an electron have opposite in direction
because the elctron is a negatively charged particle.
When we put an atom in an external magnetic field ⃗ (say along Z-axis),
then the angular momentum of vector ⃗ will precess around the field direction with
quantized components. These components can be given by
ℎ
= =ℏ
2
Fig 4. Directions of ⃗ and ⃗, when atom is kept in magnetic field ⃗.
where the ML is magnetic orbital quantum number which can have values:
ML = L, L-1, …., -L,
341
So, total number of values of ML is (2L + 1). This precession is known as 'Larmor
precession', this implies that in a magnetic field, each L-level will split in (2L + 1)
levels and each characterized by a ML value.
According to Larmor’s theorem, the angular velocity of precession is given by
⃗
= = .
⃗ 2
Interaction energy of such precession can be calculated by multiplying the angular
velocity and the projection of angular momentum ⃗ along magnetic field. In this
case it is z-component of ⃗ because magnetic field is along z-axis. So, interaction
energy is: Δ = =
eh
⇒ ΔE =
4πm
Interaction energy as a function of wave number is
Δ
−Δ = =
ℎ 4
Since, magnetic field B is uniform or same for all levels for a given atom, so, we
can write
Δ
−Δ = =
ℎ 4
Where L' is called ‘Lorentz unit’. So, for each level , change in energy from its
original level is ΔT and it is proportional to the magnetic field B. Here L' is the
wave-number separation between any two consecutive Zeeman levels for any
value of L. M L
+2
1
D2 +1
+1
1
P1 0
π
σ
NO FIELD FIELD
Fig 5. Transition 1D2 – 1P1 (L = 2 to L =1 transition)
342
Now, consider transition 1D2 – 1P1. 1D2 corresponds L = 2 and S = 0, 1P1
correspond to L = 1 and S = 0 states. So, in simple words we can say transition
from L = 2 to L = 1 transitions. In presence of weak magnetic field these will split
into (2 L + 1) levels. So, respectively it will split into 5 and 3 equidistant energy
levels. Corresponding ML values are 2, 1, 0, -1, -2; for L = 2 and 1, 0, -1 for L = 1.
There are only few optical transitions are possible. These transition rules
are known as selection rules. These rules for magnetic quantum number (ML) can
be derived by quantum mechanics. For this process selection rules are:
± 1, −
Δ =
0, −
From this rule, we get nine-transitions but Zeeman splitting is same for transitions
corresponding to ΔML correspond in wave number. So, in this case we get only
three component line which is a normal triplet pattern. From selection rules, we get
one component in the position of the field line, known as π-component and two
symmetrically displaced σ-components. Separation between consecutive Zeeman
levels is equal to the wave-number separation between consecutive components.
Wave-number separation is given by
Δ = =
4
Putting e = 1.6 × 10 C, m = 9.1 × 10-31 kg and c = 3×108 m/s,
-19
we get Δ = 46.7 B /m
where B is in Tesla (N/A-m).
Other than selection rules, quantum mechanics give us the information of
polarization rules also. Transition ΔML = 0 results in spectral line polarized with
the electric vector parallel to magnetic field (π-component). While transition
ΔML = ± 1 gives lines polarized with electric vector perpendicular to magnetic field
(σ-component).
Both σ-components together have the same intensity as the π-component
has. This intensity ratio of the components can be derived from the correspondence
principle. Thus, the normal Zeeman Effect is fully explained.
17.4
17.4 Zeeman
ZeemanEffect
EffectininHydrogen
Hydrogen
When an external magnetic field is applied, sharp spectral lines like the n=3→ 2
transition of hydrogen split into multiple closely spaced lines. This splitting comes
343
from the interaction between the magnetic field and orbital angular momentum
associated with magnetic dipole moment. In absence of the magnetic field, energy
levels in hydrogen atom depend only upon principle quantum number n. So,
emitted light will be with same wavelength.
ML
n = 3
2
1 Magnetic field off
0
–1
–2
ML
1
0
-1
n = 2
Fig 6. Zeeman splitting in Hydrogen
Here selection rules are same as in previous section. Allowed values of change in
magnetic quantum numbers ΔML are ±1 and 0.
17.5
17.5Illustrative
IllustrativeExamples
Examples
Example 1: Calculate the number of energy levels corresponding to energy level
n = 3 or E3 = −E0/9.
Sol. For hydrogen atom, energy eigenvelues depend only on principle quantum
number n. For any value of principle quantum number there are l number of
orbital angular momentum (L = 0, 1, 2, …n – 1). For every value of L, there are
2L + 1 different magnetic quantum states. So:
For n = 3: There are 3 values of L = 0, 1 , 2 and there corresponding
magnetic quantum numbers are {0},{ –1, 0, +1}, {–2, –1, 0, 1, 2} respectively.
So, there are 1 + 3 + 5 = 9 degenerate states. In absence of external
magnetic field, all states are same energy but different quantum numbers.
Example 2: Calculate the value of the Bohr magneton for energy difference
between ml = 0 and +1 components of 2P state of atomic Hydrogen placed in 2T
magnetic field.
ℏ
Sol. Bohr magneton is =
344
(1.6 × 10 )(1.05 × 10 − )
= = 9.27 × 10 /
2(9.11 × 10 )
.
So the splitting energy Δ = Δ = 1.16 × 10
17.6
17.6Self-Learning
Self-LearningExercise-I
Exercise-I
Q.1 Give electronic structure of neon. (Use standard notations).
Q.2 A hydrogen atom is placed in a 2T magnetic field. Considering normal
Zeeman Effect for splitting of n = 2 and n = 3 levels.
(a)What is the separation in energy between adjacent ML levels for the
same L?
(b)How many different wavelengths will be there for 3D to 2P transitions, if
allowed values of change in ML are only 0, ±1 ?
Q.3 An atom emits a photon with wavelength 600 nm with transition from L = 1
state to L = 0 state. Determine the shifts in the enrgy levels and in the
wavelength resulting from the interaction of the magnetic field 2T and the
atom's orbital magnetic moment.
17.7
17.7Explanation
ExplanationofofAnomalous
AnomalousZeeman
ZeemanEffect
Effect
When we look at the spectral lines, from the transition between components of
multiplet levels (closely spaced spectral lines), we get complex Zeeman pattern.
The explanation of this anomalous Zeeman Effect can be done considering electron
“spin”.
Anomalous Zeeman Effect was discovered by Thomas Preston in Dublin in 1897.
It can be observed in atoms with non-zero spin or atoms with odd number of
electrons.
It is happening because of L-S coupling which is also known as spin-orbit
interaction. Coupling of spin and angular momentum gives us total angular
momentum. According to vector model of atom, orbital angular momentum vector
and spin angular momentum precesses more rapidly about total angular
momentum ⃗. If we apply magnetic field B then ⃗ precesses about magnetic field
vector at the Larmor frequency.
When an atom is placed in a weak magnetic field, which does not decouple ⃗
and ⃗, along the Z-axis, the magnetic moment of the atom associated with the total
345
angular momentum causes the vector ⃗ to precess slowly around the magnetic field.
The motion is quantized such that the projection of ⃗ along the field direction, Jz
takes discrete values given by MJ (h/2π), where
MJ = J, J-1, J-2, …,–J.
⃗
z
⃗
⃗
Jz
⃗
µJ
⃗
⃗
Fig 7. Anomalous Zeeman Effect: total magnetic moment ⃗ (= ⃗ + ⃗) is not
exactly antiparallel to ⃗
Total values of MJ will be 2 J + 1. Due to precession of ⃗ around ⃗ we get a
small change in energy of atom and its discrete orientations break each (fine-
structure) J-level into (2 J + 1) Zeeman levels. The separation between the Zeeman
levels depends on the strength of the magnetic field and the total magnetic moment
of the atom.
To calculate the separations between Zeeman levels, let us consider the
simplest case of a single valence-electron atom. Since atom has single valence-
electron, so that valence electron is alone responsible for the angular momentum
and the magnetic moment of the atom. Classically the gyromagnetic ratio is .
Since this is the ratio of orbital magnetic moment | ⃗| and angular momentum ⃗.
346
Similarly, for studying anomalous Zeeman effect, we require ratio of spin magnetic
moment | ⃗| and spin angular momentum ⃗ . This ratio is confirmed with
quantum mechanics as twice of that of ⃗. Because of this inequality of these ratios,
total magnetic moment ⃗ (= ⃗ + ⃗) will not exactly antiparallel to ⃗.
Since total angular momentum is invariant, ⃗, ⃗, ⃗, ⃗ and ⃗ precess
around ⃗. In this precession, component of magnetic moment vector perpendicular
total angular momentum will have continual change in direction which gives
average to zero. Only parallel component remains a constant of magnitude μ .
Magnetic moment of atom is also due to parallel component. Thus
= component of ⃗ along ⃗J + component of ⃗ along ⃗
= | ⃗| cos( ⃗, ⃗) + | ⃗| cos ⃗, ⃗
= ⃗ cos ⃗, ⃗ + ⃗ cos ⃗, ⃗
But ⃗ = ( + 1)
and ⃗ = ( + 1)
So,
ℎ
= ( + 1) cos ⃗, ⃗ + ( + 1) cos ⃗, ⃗
2 2
Vectors ⃗, ⃗ and ⃗ make an obtuse-angled triangle, so using triangle property, we
have by cosine law
( ) ( ) ( )
cos ⃗, ⃗ =
( ) ( )
and
( + 1) + ( + 1) − ( + 1)
cos( ⃗, ⃗) =
2 ( + 1) ( + 1)
So,
( + 1) + ( + 1) − ( + 1) ( + 1) + ( + 1) − ( + 1)
= + ℏ
2 2( + 1) 2 ( + 1)
( + 1) + ( + 1) − ( + 1)
=
2 2 ( + 1)
( + 1) + ( + 1) − ( + 1)
+ ( + 1)ℏ
( + 1)
347
( + 1) + ( + 1) − ( + 1)
= 1+
2 2 ( + 1)
( + 1) + ( + 1) − ( + 1)
+ ( + 1)ℏ
2 ( + 1)
The quantity inside the brackets was first described by Alfred Lande in 1921. It is
named after him and known as ‘Lande g-factor’, that is
( + 1) + ( + 1) − ( + 1) ℎ
= 1+ ( + 1)
2 2 ( + 1) 2
Relative separation of Zeeman levels for different terms can be directly explained
with g-factor. The expression for g-factor for a multi-electron atom under L-S
coupling is same as explained in previous sections.
The expression for the total magnetic moment of the atom now becomes
ℎ
= ( + 1) = ⃗.
2 2 2
Let us now calculate the magnetic interaction energy. From the previous
expression, we get
= .
⃗ 2
So, ratio of total magnetic moment to the total angular momentum in states can be
determined by g ,where the angular momentum is partly orbital and partly spins.
(for S = 0 and so J= L, g = 1; for L = 0 and so J = S, g =2).
From Larmor's theorem, angular velocity (or angular frequency) of
precession of ⃗J around the magnetic field B⃗ is
= = .
⃗ 2
The energy of precession is equal to product of the projection of ⃗J along B⃗ and the
angular velocity. In our case magnetic field is along Z-axis, so projection of total
angular momentum along magnetic field is the z-component of total angular
momentum. That is :
ℎ
= .
2
Thus Δ = =
ℎ
⇒Δ = .
2
348
Interaction energy, in terms of wave-number is
Δ
−Δ = = .
ℎ 4
Here is the Lorentz unit L'. Thus
− = ′.
This is the expression the Zeeman shift of a single valance electron system. This is
also for the weak-field magnetic interaction energy. The expression for the atoms
having two or more valence electrons under L–S coupling is same as one-electron
system. For one-electron system, we can see that each J-level splits into (2 J + 1)
equal energy spaced Zeeman levels corresponding to the possible values of MJ.
The Zeeman splitting depends on the value of g for different levels or we can say it
is different for different J-levels. This means that the relative separations of the
Zeeman levels of one term and those of another can be determined by the g-factor
alone.
Let us consider the Zeeman splitting of sodium of the resonance lines D1
and D2. These lines arise from the transitions
2 → 2 and 2 → 2
We know that
( + 1) + ( + 1) − ( + 1)
= 1+
2 ( + 1)
So, the Zeeman levels, g-factors and the Zeeman shifts for the involving terms in
these transitions are as follows:
Terms No. of Zeeman g Shift in
levels (+J, …. J) Lorentz unit
(2J+1)
2 2 2 4 ±1
1 1 3
= 0, = =
2, 2
2 2 2 4 1
±
3 3 3
1 1
= 1, = =
2, 2
349
2 4 4 3 1 2
± ,± ±2, ±
3 2 2 3
1 3
= 1, = =
2, 2
The splitting of these terms has been displayed in figure bellow:
MJ gMJ
3/2 2
2 1/2 2/3
P3/2
–1/2 –2/3
–3/2 –2
2 1/2 1/3
P1/2
–1/2 –1/3
D1 D2
2
1/2 1
S1/2 –1/2 –1
π
D1 D2
Fig 8. 2 → 2 2 → 2 .
Applying the selection rules
= 0, ±1 (but =0↮ = 0 if = 0)
We obtain that the D1 line will split in four Zeeman components and the D2 line
splits in six components. The components corresponding to Δ = 0 will polarize
with electric vector perpendicular to the field (σ-components).
The intensities of the Zeeman components given by following rules:
(i) The sum of all the transitions starting from any initial Zeeman level is equal to
the sum of all transitions starting from any other level having the same
350
principle quantum number n and azimuthal quantum number l values.
(ii) The sum of all transitions arriving at any Zeeman level is equal to the sum of
all transitions arriving at any other level having the same principle and
azimuthal values.
17.8
17.8 Zeeman
ZeemanEffect
EffectininSodium
Sodium
Sodium light consists bright doublet which is responsible for the bright yellow
light. This can be used to demonstrate several influences. From this we can study
splitting of the emission lines of atomic spectra. We get doublet from the transition
from 3P to 3S levels. These are same as in hydrogen atom. Since principal
quantum number is same and only there is a change in orbital quantum number.
3S (orbital quantum number is 0) is lower than the 3P (L = 1). So, it is also a good
example of the dependence of atomic energy levels on angular momentum. The 3S
electron is effectively less shielded than the 3P electron, so the 3S level is more
tightly bound. Here doublet shows the smaller dependence of the atomic energy
levels on the total angular momentum. Because of magnetic energy of the electron
spin, in the presence of the internal magnetic field caused by orbital motion, the 3P
level splits into two states with total angular momentum J = 3/2 and J = ½. This
effect is known as spin-orbit effect. If we apply additional external magnetic field,
these levels will split further by the magnetic interaction. It depends on the
energies on the z-component of the total angular momentum. This splitting gives
the Zeeman effect for sodium.
17.9
17.9Paschen-Back
Paschen-BackEffect
Effect
Paschen-Back Effect is the splitting of atomic energy levels in the presence
of strong magnetic field. To observe this effect magnetic field should be
sufficiently large to disrupt the coupling of orbital angular momentum and spin
angular momentum.
External magnetic field in the Zeeman Effect is weak in comparison to the internal
fields due to spin angular momentum and orbital motion of valence electrons of
atom. However the strength of external magnetic field is not sufficient to disrupt
spin-orbit coupling. If we increase the strength of external magnetic field,
separations between multiplet fine structure components increase. For more
magnetic field it will increase more and up to the separation become greater than
351
fine-structure components. The anomalous Zeeman pattern then changes again like
a normal Zeeman pattern. This is the condition when spin-orbit coupling is
disrupted by external magnetic field. This process can be explained in the
following way: ⃗
z
⃗ Sz
Lz ⃗
Fig 9. Cartoon diagram for showing respective direction of ⃗ and ⃗ and their
components.
When we apply external magnetic field stronger than the internal fields, the
magnetic coupling between total angular momentum and external magnetic field
exceeds the coupling of spin-orbit. The precession of ⃗ about ⃗ become faster
then ⃗ and ⃗ precession about ⃗. When we apply these conditions than ⃗ − ⃗
coupling will partially break down which implies that ⃗ is not fixed in magnitude
any more. If we increase magnetic field ⃗ more than ⃗ and ⃗ start precessing
independently about ⃗. In this state their quantized components along field
direction (here we took it in Z-axis) will be L and . Magnitudes of these
components will be ℏ and M ℏ respectively and magnetic quantum numbers
M and M will have discrete values as follows:
= , − 1, − 2, … . , −
and = , − 1, − 2, … . , −
By Larmor's theorem, the angular velocities of any precession are given by the
product of magnetic field and corresponding ratio of magnetic moments with the
angular momenta. So for ⃗ and ⃗
= and =2
2 2
352
Since the energy of any precession is equal to the product of the projection of the
corresponding angular momentum vector along the magnetic field direction and
angular velocity. That is
ℎ
ΔE = =
2 2
and ΔE = =2
Main energy shift ΔE from unperturbed energy level is the sum of these two
interaction energies. So,
Δ =Δ +Δ
=( +2 ) ,
4
Or in Lorentz unit of ,
−Δ = ( +2 ) ′
This expression is for strong magnetic field interaction energy, where we
ignore spin-orbit interaction at all. It shows that each free level will shift into
(2L + 1)(2S + 1) magnetic levels. Because(2L + 1) values comes from M and
(2S + 1) from M .
As a specific example, in strong magnetic field, let us consider the transitions
2P → 2S
This transition is responsible for the D1 and D2 lines of sodium 2P → 2S . In
presence of strong magnetic field, these levels and magnetic shifts for multiplet
terms are given in following table:
Term No. of strong-field Shift in Lorentz
levels unit ( + 2 )
(2 + 1)(2 + 1)
2 6 1, ½, - ½ 2, 0
P = 1, =
0 ½, - ½ 1, ‒1
-1 ½, - ½ 0, ‒2
2 2 0 ½, - ½
S = 0, = 1, ‒1
The strong-field splitting of the terms and have been shown in figure bellow:
353
(ML + 2MS) ML MS
2 2 1 ½
P3/2
1 0 ½
2 0, 0 –1,1 ½, –½
P
2 –1 0 –½
P1/2 –2 –1 –½
1 0 ½
2
S
–1 0 –½
π
σ σ
Fig 10.Strong field splitting of the terms 2P and 2S
Selection rules in presence of a strong field for above transitions are:
ΔM = 0 (Components polarized parallel to the field)
ΔM = ±1 (Components polarized perpendicular to the field)
ΔM = 0.
When these selection rules are applied we get a pattern same as a normal Zeeman
triplet.
Spit-Orbit Correction: In practice, the residual spin-orbit coupling changes the
relative energies of the components of different terms. Due to this we can add a
small term aM M in the expression for the magnetic interaction energy. Now
interaction energy in Lorentz term will become
−ΔT = (M + 2M )L′ + aM M .
This implies that each of two σ-components of normal Zeeman triplet will split in
narrow doublet, triplet and so on. In this 2P → 2S transition, each σ-component
will split into a doublet with a separation just two-thirds that of the field-free
double.
354
π
Fig 11. Strong-Field Pattern with Spin-Orbit Coupling
Experimentally, the Paschen-Back effect has been observed for very narrow
multiplets only. For example Li doublet having a field-free separation of
0.34 .Since ordinarily available magnetic field, for example 4.3Tesla magnetic
field can produce a magnetic splitting of about 2 and Paschen-Back Effect
occurs when the magnetic splitting exceeds the fine-structure (field-free) splitting.
So, for Li doublet it is larger than the fine-structure splitting. Because of this
Paschen-Back effect can easily be observed. For sodium resonance doublet
(17 ) fine-structure splitting is much higher. So, to observe this effect in
sodium, we need an abnormally large field.
Here we have already considered the cases when the external field is either
very weak (Zeeman effect) or very strong (Paschen-Back effect) as compared to
the internal field in the atom. For intermediate fields (comparable with internal
field) complicated patterns are obtained.
17.10
17.10Transitions
Transitionsfrom
fromWeak
WeaktotoStrong
StrongField
Field
The number of magnetic levels into which a given state is split doesn’t
depend on the magnetic field strength. This number is called the ‘quantum weight’.
In a weak field, a level with a given inner quantum number J will split into
(2 + 1)levels where orientations of J in external magnetic field is (2 + 1). In
case of an atom with one valance electron, J can have only two values + and
− , so that level will split into
1 1
2 + +1 + 2 − +1 =4 +2
2 2
levels. In a strong field, L alone has (2 + 1)orientations and for each of these, S
has (2 + 1), giving altogether
(2 + 1)(2 + 1) = 4 + 2 [Since S = ½]
levels, same as in a weak field.
355
ML MS
MJ +1 +½
3/2
½ 0 +½
2
P3/2 –½
–1 +½
–3 /2
2 ½
+1 –½
P1/2 –½
0 –½
–1 –½
0 +½
2
S1/2
0 –½
Fig12.Transition of the magnetic levels corresponding to the states 2S½,2P½ and 2P3/2.
In a weak field, we characterize each of the magnetic levels by the quantum
numbers J and MJ while in a strong field ML and MS are the characteristic quantum
numbers. Now, we have to look at the levels J and MJ , which reread a particular
level with ML and MS when the field is increased. Here, things to be noted that the
sum of the projections of the angular momentum vectors on magnetic field does
not change. In presence of weak field this projection is MJ and in presence of a
strong magnetic field it is ML+ MS. Hence the first rule of transition is
= +
This is insufficient to correlate all weak and strong field levels. Since there
are cases when there are more than one level with the same value of MJ. Hence
next restriction is that there will not be any two levels with the same MJ cross each
other.
17.11
17.11Zeeman
ZeemanEffect
EffectininSome
SomeTransitions
Transitions(examples)
(examples)
(i) 1F3 − 1D2 : It is a singlet-singlet transition. It will give a normal Zeeman
triplet.
356
ML
+3
+2
+1
1 0
F
–1
–2
–3
+2
+1
1 0
D
–1
–2
π
σ σ
NO FIELD FIELD
Fig 13.Splitting of 1F3 – 1D2, single-singlet transition.
The terms 1F and 1D correspond to L = 3 and L = 2 respectively. In presence of a
weak magnetic field it will break into (2L + 1) = 7 and 5 Zeeman components
respectively. The values characterizing the Zeeman levels are 3, 2, 1, 0, -1, -2,
-3 and 2, 1, 0, -1, -2 respectively.
Since for singlet terms (S = 0, J = L) the Lande g-factor is 1. The separation
between consecutive Zeeman levels is the same for both terms equal to one
Lorentz unit. The splitting of the terms is shown in figure .
The selection rules Δ = 0, ±1. From these rules we get 15 transitions. Since
the Zeeman splitting is same for both terms so, all transitions corresponding to
same
357
Δ coincide in wave number. Hence we obtain only three Zeeman component
lines; the π-component corresponding to Δ = 0 and two π-components
corresponding to Δ = ±1 . This is normal Zeeman triplet.
(ii) − : It is a doublet-doublet transition. So, the Zeeman pattern would
be anomalous. The weak-field interaction energy of a one-electron atom is given
by
= ′,
where L' is the Lorentz unit. The Lande g-factor is
( + 1) + ( + 1) − ( + 1)
= 1+
2 ( + 1)
The Zeeman levels, g-factors and the Zeeman shifts for the given terms 2 and
2 are as follows:
Term No. of Zeeman g Shift in L' unit g
levels (+J, …. –J) MJ
(2J +1)
2 2 2 1 1 1 1
,− ,−
3 2 2 3 3
1 1
= 1, = , =
2 2
2 4 4 2 6 2 2 6
, ,− ,−
5 3 5 5 5 5
1 3
= 2, = , =
2 2
The splitting of these terms has been displayed in figure14:
The selection rule is = 0, ±1.
There are in all six allowed transitions ,hence six Zeeman components. Transitions
corresponding to Δ = 0 give π-components polarized parallel to the magnetic
field and transitions corresponding to Δ = ±1 give σ-components polarized
perpendicular to the field as shown in the energy level diagram.
358
MJ gMJ
3/2 6/5
2
½ 2/5
D3/2 –½ –2/5
–3/2 –6/5
½ 2/5
2
P1/2 –½ –2/5
σ
Fig 14. Zeeman shifts for the given terms 2 and 2 , doublet-doublet transition
(iii) − : It is again a doublet-doublet transition so that the Zeeman
pattern would be anomalous.
The Zeeman levels, g-factors and the Zeeman shift for the given terms 2 and
2 are as follows:
Term No. of g MJ Shift in L' unit
Zeeman (+J, …. –J) g MJ
levels
(2J +1)
2 4 4 3 1 1 3 6 2 2 6
, ,− ,− , ,− ,−
3 2 2 2 2 3 3 3 3
1 3
= 1, = , =
2 2
2 6 6 5 3 1 1 3 5 15 9 3 9 15
, , ,− ,− ,− , , ,− ,−
5 2 2 2 2 2 2 5 5 5 5 5
1 5
= 2, = , =
2 2
359
The splitting of these terms has been displayed in figure given bellow:
MJ gMJ
5/2 15/5
3/2 9/5
2
D5/2 ½ 3/5
–½ –3/5
–3/2 –9/5
–5/2 –15/5
3/2 6/3
2
P3/2 ½ 2/3
–½ –2/3
–3/2 –6/3
π
σ
Fig 15.Double-doublet transition 2D5/2 – 2P3/2. The complete Zeeman pattern of 12
components
The selection rule in operation is = 0, ±1.
There are four allowed transitions corresponding to Δ = 0 which give
π-components while the all four transitions each corresponding to = ±1 give
σ-components.
(iv) Principal Series Triplet 3P – 2S or , , − : The fine-structure
transitions are:
3 −3 ; 3 −3 ; 3 −3
360
The g-factor and Zeeman shifts for the unperturbed levels 3 , 3 , 3 and 3
are as follows:
Unperturbed level No. of MJ (+J, … -J) Shift in Lorentz unit
Zeeman
levels
(2J+1)
3 1 0 0 0
(L = 1, S = 1, J = 0) 0
3 3 3 1, 0, – 1 3 3
, 0, −
(L = 1, S = 1, J = 1) 2 2 2
3 5 3 2, 1, 0, ‒ 1, ‒ 2 6 3 3 6
, , 0, − , −
(L = 1, S = 1, J = 2) 2 2 2 2 2
3 3 2 1, 0, ‒ 1 2, 0, -2
(L = 0, S = 1, J = 1)
The magnetic splitting of levels is shown in figure bellow:
MJ gMJ
2 6/2
MJ gMJ 3 1 3/2
1 3/2 P2 0 0
3 0 0 (g =3/2)
3
MJ gMJ P1 –1 –3/2
P0 (g = 2)
3 –1 –3/2 –2 –6/2
0 0
3 1 2 3 1 2 3 1 2
S0 0 0 S0 0 0 S0 0 0
(g= 2) –1 –2 (g= 2) –1 –2 (g= 2) –1 –2
π π π
σ σ σ
(a) (b) (c)
Fig 16. Splitting of 3P0,1,2 and 3S1 level in magnetic field.
361
From selection rules = 0, ±1 (but =0↮ = 0 if = 0) we get, three
Zeeman components in the transition 3 − 3 ; six in 3 − 3 and nine in
3
P2 – 3S1. The Zeeman transition = 0 → = 0 in 3 − 3 is forbidden.
Since, at the same time = 0. This transition is indicated by a dotted line in
figure.)
Energy-level diagram for the Zeeman patterns are shown in figure. While
the qualitative structure of each pattern depends only on two unperturbed levels for
the values of J. The energy separations depend on g and hence on other properties
like coupling conditions and on other quantum numbers.
All the three patterns in this transition are symmetrical with regard to wave
number, intensity and polarization of the components. The π-components form a
central group and polarized with electric vector parallel to magnetic field. The
σ-components form two symmetrically displaced groups and the components are
equidistant in each and electric vector perpendicular to the field. The sum of the
intensities of the π-components are equal to that of the σ-components.
(v) − : It is a triplet-triplet transition. It would give an anomalous
Zeeman pattern in a ‘weak’ external magnetic field. The Zeeman shifts of the
various forms an unperturbed level are given by
−Δ = ′,
where L' is the Lorentz unit and g is given by
( + 1) + ( + 1) − ( + 1)
= 1+
2 ( + 1)
The Zeeman levels, g-factors and the shifts from the given unperturbed levels 3
and 3 are given in following table:
Unperturbed level No. of Zeeman G (+ , . . . , − ) Shift in Lorentz unit
levels
(2J + 1)
3 5 7 2, 1, 0, -1, -2 14 7 7 14
, , 0, − , −
(L = 2, S = 1, J = 2) 6 6 6 6 6
3 3 3 1, 0, -1 3 3
, 0, −
(L = 1, S = 1, J = 1) 2 2 2
362
MJ gMJ
2 14/6
1 7/6
3
D2 0 0
–1 –7/6
–2 –14/6
1 3/2
3
P1 0 0
–1 –3/2
π
σ
Fig 17.Triplet-triplet transition 3P1 - 3D2
From selection rules = 0, ±1 ( =0↮ = 0 if = 0) we get 9 allowed
transitions. = ±1 each give three components. The complete pattern with
Zeeman splitting of the levels 3D2 and 3P1 isfigure.
(vi) − : This is also a triplet-triplet transition. This would give an
anomalous Zeeman pattern in a ‘weak’ external magnetic field.
Zeeman levels, g factors and the shifts from the unperturbed levels 3 and
3 are given in following table:
Unperturbed No. of g Zeeman Shift in Lorentz
level Zeeman (+ , . . . , − ) Unit
levels
(2J + 1)
3 7 4 3, 2, 1, 0, -1, -2, -3 12 8 4 4 8 12
, , , 0, − , − , −
= 2, = 1, 3 3 3 3 3 3 4
=3
363
3 5 3 2, 1, 0, -1, -2 6 3 3 6
, , 0, − , −
= 1, = 1, 2 2 2 2 2
=2
The splitting of these levels are shown in figure bellow:
From selection rules = 0, ±1 ( = 0 ↮ = 0 if = 0) we get, 15 allowed
transitions. From the rule Δ = ±1 we get, five σ-components. The complete
pattern is shown in the energy-level diagram.
MJ gMJ
3 12/3
2 8/3
1 4/3
3 0 0
D3
–1 –4/3
–2 –8/3
–3 –12/3
2 6/2
1 3/2
3 0 0
P2
–1 –3/2
–2 –6/2
π
σ σ
Fig 18.Splitting of 3D3 – 3P2 levels.
7.12Illustrative
7.12 IllustrativeExamples
Examples
Example-3: Calculate the distance between Zeeman components of a spectral line
of wavelength 4500 Å. If a sample of a certain element is kept in a magnetic field.
Given Flux density 0.3 Tesla, e/m = 1.76 × 1011 C/kg, c = 3 × 108 m/s.
364
Sol. The wave-number separation between the components of a normal Zeeman
triplet is given by
= =
4 4
Putting the given values, we get
(1.76 × 10 ⁄ )0.3 ⁄ −
=
4 × 3.14 × (3.0 × 10 ⁄ )
= 14.0
Now, =1
or + =0
or | |= =
= (4500 × 10 ) (14.0 )
= 283.5 × 10
= 0.02835 Å
Example-4: Evaluate the Lande g-factor in the 2p3s configuration for the 3P1 of
the atom and use the result to predict the splitting of the level. Atom is in an
external magnetic field of 0.1 Tesla.
Sol. For the 3 level, we have
= 1, = 1, = 1,
( ) ( ) ( )
So =1+ ( )
1(1 + 1) − 1(1 + 1) + 1(1 + 1)
=1+
2 × 1(1 + 1)
1 3
=1+ =
2 2
For J = 1, the possible values of MJ are 1, 0, -1 and so the level is split into three
components. The wave-number shift of the components is given by
=
4
The Zeeman level corresponding to M =0 remains unshifted while those
corresponding to M = ±1 are shifted by
=±
4
365
3 (1.6 × 10 )(0.1 ⁄ − )
=±
2 4 × 3.14 × (9.1 × 10 )(3 × 10 ⁄ )
= ±7.0
= ±0.07
17.13
17.13Self-Learning
Self-LearningExercise-II
Exercise-II
Q.1 Calculate the effective magnetic field experienced by the electron in the 3P
levels of sodium atom.
Q.2 Suppose the sodium D1 line emitted in a magnetic field is observed to be
split into 4-components. What is the magnetic field B ? (Given values are:
Wavelength difference = 0.022 nm, D1 line is at 589.5 nm)
Q.3 Calculate the number of energy levels corresponding to energy level n = 2 or
E3 = -E0/4.
Q.4 Calculate the number of transitions between 1D2 and 1P1 states due to
normal Zeeman Effect.
17.14
17.14Summary
Summary
American solar astronomer George Ellery Hale observed Zeeman Effect in the
solar spectra in 1908. This sprctra indicate the existence of strong magnetic fields
in sunspots. Such fields can be of the order of 0.1 Tesla or higher. Zeeman Effect is
utilized in many laser cooling applications such as a magneto-optical trap and the
Zeeman slower. Zeeman Effect is also useful to measure magnetic field strength
and orientations in Tokamak plasma. It can also measure temperature from
Zeeman components.
17.15Glossary
17.15 Glossary
Multiplet : A group of spectral lines.
LS coupling : Coupling of angular momentum and spin angular momentum of an
electron.
Bohr magneton : A physical constant (it can be different for spin and angular).
Selection rules : Constrains of the possible transitions of from one quantum state
to another.
Zeeman energy : Potential energy of magnetized particles in external magnetic
field.
366
g factor : Dimensionless quantity for magnetic moment and gyromagnetic ratio.
17.16Answers
17.16 AnswerstotoSelf-Learning
Self-LearningExercises
Exercises
Answers to Self-Learning Exercise- I
Ans.1: 1S2 2S2 2P6
Ans.2: (a) 1 and 9.274× 10–24 J/T (b) 9
Ans.3: Wavelength shift = 0.034 nm
Answers to Self-Learning Exercise- II
Ans.1: 18 T
Ans.2: 0.51 T = 5100 Gauss
Ans.3: 6
Ans.4: 9 (will give only 3 spectral lines.)
17.17
17.17Exercise
Exercise
Q.1 Describe an experimental set-up to study Zeeman Effect.
Q.2 What do you understand by anomalous Zeeman Effect ? Discuss the
Zeeman pattern of the resonance (D1 , D2) lines for sodium.
Q.3 Distinguish between normal Zeeman, anomalous Zeeman and Paschen-Back
effects. Determine the Lande g-values for the various levels of multiplets.
Q.4 Calculate splitting of term 4D½ in arbitrary magnetic field.
Q.5 In one electron atom, determine Zeeman transition line for 2D3/2 – 2P3/2.
Q.6 In one electron atom, determine Zeeman transition line in 2D5/2 – 2P3/2.
Q.7 Calculate g-factor for 3P term.
Q.8 Write down the number of Zeeman levels (2J + 1) for 2P3/2 term.
Q.9 Write down the values of L, S and J for 2D5/2 term.
Q.10 What are the possible values of MJ for 2P3/2.
17.18Answers
17.18 AnswerstotoExercise
Exercise
Ans.1: See section 17.2.
Ans.2: See section 17.7 and 17.8
367
Ans.3: See section 17.9
Ans.4: 0
Ans.5: 10
Ans.6: 12
Ans.7: 3P0,1,2 : g = 0/0. 3/2, 3/2
Ans.8: 4
Ans.9: L = 2, S = ½, J = 5/2.
Ans.10: ±3/2, ±1/2.
Referencesand
References andSuggested
SuggestedReadings
Readings
1. Nobel Lectures: Physics, Vol. 1, Elsevier, Amsterdam, 1967.
2. R. Eisberg and R. Resnick, Quantum Physics of Atoms, Molecules, Solids,
Nuclei and Particles. 2nd ed., Wiley, New York, 1985.
3. W. A. Hilton, Am. J. Phys. 30, 724 (1962).
4. Feynman, Richard P., Leighton, Robert B., Sands, Matthew (1965). The
Feynman Lectures on Physics 3. Addison-Wesley. ISBN 0201021153
368
UNIT-18
The
The Stark
Stark Effect
Effect and
and
Hyperfine Structure
Hyperfine Structure of
of Spectral
Spectral Lines
Lines
Structure of the Unit
18.0 Objectives
18.1 Introduction
18.2 Stark Effect of Hydrogen atom
18.3 Weak-Field Stark Effect in Hydrogen
18.4 Strong-Field Stark Effect in Hydrogen
18.5 Hyperfine structure of spectral lines
18.6 Isotope effects
18.7 Illustrative Examples
18.8 Self-Learning Exercise – I
18.9 Nuclear spin and hyperfine splitting
18.10 Intensity ratio and determination of Nuclear spin
18.11 Back Goudsmit effect in hyperfine structure
18.12 Illustrative Examples
18.13 Self-Learning Exercise – II
18.14 Summary
18.15 Glossary
18.16 Answers to Self-Learning Exercises
18.17 Exercise
18.18 Answers to Exercise
References and Suggested Readings
369
18.0
18.0Objectives
Objectives
In 1913, German physicist Johannes Stark studied Hydrogen atom emission in
electric field of a condenser. In presence of external electric field (of the order of
105 V/cm), he observed the shifting and a splitting of the spectral lines of the
Balmer series of hydrogen (emission spectra). Observable amount of splitting or
shifting is known as Stark shift. It is also known as Stark splitting. In previous
chapter, we have already studied Zeeman Effect where a spectral line split into
several components due to external magnetic field; similarly Stark effect is electric
analogue of Zeeman Effect.
18.1
18.1Introduction
Introduction
The Strak Effect is a result of interaction of external electric field with electric
moment of the atom. Interaction energy can be defined as = − ⃗. ⃗
where ⃗is the electric dipole momentof electron in atom. Electric dipole moment
comes in picture because of charge distribution and it can be calculated with the
charge distribution. Here we will study two aspects of the Stark Effect: the linear
effect and the quadratic effect. Here we will see that the linear effect is due to a
dipole moment which is induced by the external electric field. For simplicity fine
and hyperfine structure effect will be neglected. We can explain and study the
molecule formation from atoms, broadening of spectral lines and dielectric
constants with the study of Stark Effect.
18.2
18.2Stark
StarkEffect
EffectofofHydrogen
HydrogenAtom
Atom
In Stark Effect, if we take observations from different positions, then we get some
different results. In particular and for simplicity we look at perpendicular and
parallel to the applied electric field. When we look at perpendicular to electric field
then we get two plane-polarized lines or components. One component is parallel to
electric field vector, called π – component and another is perpendicular to electric
field vector, called σ – component. If we observe parallel to electric field then we
get only one unpolarized component, known as σ– component. Few initial
observations of Stark Effect are as:
370
(i) In general, all hydrogen lines are in symmetrical patterns but the pattern
mainly depends on the principal quantum number n. Number of Stark lines
and width of pattern increases with n.
(ii) Wavenumber shifts are same for all hydrogen lines. It is integral multiples
of a unit which is proportional to the strength of the electric field.
(iii) Polarization properties of Stark lines are same as Zeeman lines. Only, the π–
component shows more shift than the σ– component.
(iv) Ordering of Stark components is in the increasing order of principal
quantum number n as H , H , H.
(v) For lower energy states symmetrical splitting is proportional to the field
intensity and for higher states Stark components show unidirectional
displacements proportional to the square of the field strength. This is called
second-order Stark Effect.
18.3Weak-field
18.3 Weak-fieldStark
StarkEffect
EffectininHydrogen
Hydrogen
Since, orbital angular momentum ⃗ and spin angular momentum ⃗ of the electron
of a hydrogen atom have magnetic interaction. When we apply an external electric
field ⃗ ,then it will interact with total angular momentum ⃗. If field interaction
energy with electron’s total angular momentum is less than the magnetic
interaction energy between orbital momentum and spin momentum then the Stark
splitting will be much smaller compared with the fine-structure splitting. Such a
field is known as weak-field.
µ
mj
j
l
Fig 19.Schematic diagram of l-s coupling
371
We get ⃗ by the coupling of ⃗ and ⃗. Therefore ⃗ precesses around ⃗ with
projection mj h/2π,
= +, − 1, − 2, … , − .
So, unlike the Zeeman levels, the Stark levels +mj and –mj arise from a given
unperturbed level which have same energy.
Selection rules for weak-field Stark effect are the same as those for the Zeeman
effect, that is
Δ = 0 gives π components
Δ = ±1 gives σ
components
Following these selection rules, each of the fine-structure components I, II, III, IV,
V in H should show a symmetrical Stark pattern. The weak-field Stark pattern has
never been observed.
mj
NO FIELD WEAK FIELD 1 3 5
D5/2 ± , ,
2 2 2
3 1 1 3
± , , ,
n=3 P3/2, D3/2 2 2 2 2
½
S½, P½ ½
2P3/2 1/2, 3/2
n=2 ½
2P½ , 2S½ ½
π
I II III IV V σ
Fine-structure of H Weak-field Stark splitting of H components
Fig 20. Energy levels of H-atom for the transitions n = 3 and n = 2.
372
18.4
18.4Strong-Field
Strong-FieldStark
StarkEffect
EffectininHydrogen
Hydrogen
When we apply an electric field ⃗ on hydrogen which has the interaction energy
with electron’s angular moment ⃗ , such that it is greater than the magnetic
interaction energy between electron’s orbital momentum ⃗ and spin momentum ⃗.
Therefore, the Stark splitting of the energy levels due to the electric field will be
larger than the fine-structure splitting. This is known as the ‘strong’ field for which
first-order Stark effect in hydrogen has actually been observed. In such strong
field, magnetic coupling between ⃗ and ⃗ is breakdown and ⃗ get quantized. It
precesses independently around the applied electric field ⃗ . The spin is however
not acted on by ⃗ .
In 1916, German physicists Karl Schwarzchild and Russian-American physicists
Paul Sophus Epstein independently explained the observation of first-order Stark
Effect in hydrogen and they explained the same for ionized helium by quantizing a
hydrogen-like atom in an electric field. At that time electron spin was not
discovered. For this explanation, they used Bohr-Sommerfeld quantum theory,
which is known as old quantum theory. This was taken an outstanding triumph for
the old quantum theory because the results given by this theory were very little
altered by quantum mechanical treatment.
Let an electron is moving in a Kepler ellipse. If we will apply homogeneous
electric field ⃗ along z-axis than it will behave differ than magnetic field. If we
average the center of gravity of the electron for the Kepler motion then it will not
coincide with the nucleus which forms an electric dipole. Electric field applies a
torque on the orbital dipole which causes a precession of the orbital about the z-
axis. However, in presence of magnetic field the orbital angular momentum ⃗ is
not a constant and the orbital quantum number l is no longer a “good” quantum
number. The projection of ⃗ along electric field (z-axis) is lz , given by ml h/2π,
where ml is the electric quantum number. lz is still a constant of motion and ml
retains its strict meaning. Energy value in parabolic coordinates depends on field-
free energy of atom E0 , Bohr radius a0 , principle quantum number n and two new
parabolic quantum numbers n1 and n2. These parabolic quantum numbers are
defined as:
373
= − − −1
z
F
l
lz min
max
n2
min
n1
max
Fig 21.Precession of the orbital about z-axis or field axis.
Since, allowed values are
= 1, 2, 3, … . ∞
= 0, ±1, ±2, … . , ±( − 1)
= 0, 1, 2, 3, … . , − 1
= 0, 1, 2, 3, … . , − 1
n1 limits the electron’s motion to the region between the two paraboloids of
revolution and max ; while n2 limits it to the region intersected by the two pairs
of paraboloids, the electron has three periodic motions, one around the field ⃗
given by ml and one each along the and coordinates given by n1 and n2. Since
the last two periods are not necessarily the same, the orbit is not closed and the
electron in time covers every point in the intersected region.
18.5
18.5Illustrative
IllustrativeExamples
Examples
Example1. Prove that the Stark-shift for the ground state (n = 1) of hydrogen is
zero.
Sol. Shift is given by the
374
Δ 3
−Δ = = ( − )
ℎ 2 ℎ
Putting the values of a0 , e, h, c and Z (=1 for H-atom)we get
3 × 0.53 × 10 × 1.6 × 10
−Δ = ( − )
2 × 6.63 × 10 × 3 × 10
= 6.4 × 10 ( − ) .
(Here field F is expressed in Volt/cm.)
Allowed values of n , n2 and n1 can be get from m = n – n2 – n1 – 1. Here m = 0,
n = 1. So, n2 – n1 = 0. This implies that the Stark-shift for ground state of hydrogen
is zero.
Example 2. Excluding nuclear spin, write down the configuration of n = 2 in
hydrogen atom.
Sol. For a given j there are 2j + 1 degenerate sublevels can be written:
2S½ |2S½, + ½ , |2S½, –½
2P½ |2P½, + ½ , |2P½, –½
2P3/2 |2P3/2, + 3/2, |2P3/2, + 1/2, |2P3/2, –½, |2P3/2, –3/2
When angular momentum and spin will not couple (strong field) then these
levels will split as given bellow:
|2S1/2, 1/2= |2S, 0⊗| ½
|2P1/2, 1/2 = (1/√3)|2P, 0⊗|1/2 – √(2/3) |2P, 1⊗|∓1/2〉
|2P3/2, 1/2 = √(2/3) |2P, 0⊗|1/2〉 + (1/√3)|2P, 1⊗|∓1/2
|2P3/2, 3/2 = |2P, 1⊗|1/2
18.6Hyperfine
18.6 HyperfineStructure
StructureofofSpectral
SpectralLines
Lines
When we increase the resolution of instruments by taking high resolution
instruments to observe the Stark Effect, we get further splitting into more
components. Order of this splitting is very much smaller than ordinary splitting
multiplet. This further splitting is known as ‘hyperfine structure’ and it is caused
by properties of the atomic nucleus.
375
To study hyperfine structure experimentally, we need a light source which gives
extremely sharp lines. In hyperfine structure, there are two types of nuclear effects.
First is the presence of isotopic species in the given sample or study element.
Isotope produces spectral lines at slightly different wavenumbers relative to each
other. Second type of effect comes from charged nucleus possesses as spin angular
momentum and the associated magnetic dipole moment. Hyperfine splitting of the
spectral terms comes from the interaction between internal magnetic field
(produced by orbital motion of electron) of atom and spin magnetic dipole moment
of the nucleus.
18.7
18.7Isotope
IsotopeEffects
Effects
Many elements have different contents of isotopic atoms. Since, different isotopes
of an element have same number and same arrangement of extra-nuclear electrons.
But isotopes have different masses from each other. Since Rydberg constant for an
atom depends on the nuclear mass, through the reduced mass of the atom. Different
isotopes have slightly different values of Rydberg constant. Correspondingly, the
same transitions in different isotopes give rise to slightly different wavenumbers.
In hydrogen atom variation in Rydberg constant can be observed easily. First four
members of Balmer series, H , H , H and H (each) has a very weak companion
on the short-wavelength side at distances of 1.79, 1.33, 1.19 and 1.12 Å
respectively. These shifts agree with the theoretical values if the companions are
attributed as due to presence of an isotope of mass 2 (deuterium) and it was in this
way that the existence of heavy hydrogen was first established.
Hydrogen isotope shift is the simplest case. Many cases of isotope-shift are not as
simple. In many earths and heavier atoms, isotope shift comes due to their different
radii with masses, not due to their masses only. These calculations can be
understood purely with Columbian interaction.
18.8Self-Learning
18.8 Self-LearningExercise-
Exercise-I I
Q.1 Write down the degenerate states in n = 3 subspace.
Q.2 Write down the first order stark splitting of the level n = 3 for hydrogen.
Q.3 A particle of charge q and mass m, which is moving in a one-dimensional
376
harmonic potential of frequency , is subjected to a weak electric field E in
z-direction.
a. Find expression for energy.
b. Calculate the energy to first nonzero correction and compare it with
above result.
18.9
18.9Illustrative
IllustrativeExamples
Examples
Example 1 Calculate the shift for H line (4861.33 Å).
Sol. For this transition, we have from Balmer’s formula
1 1 1
= −
2 4
1 1 1
= −
2 4
So,
=
− −
=
−
Δ = − = −
109707.4 cm − 109677.6
= −4861.33 Å
109707.4
= −1.32 Å
Example 2: An atom with nuclear spin is I = 3, have 2 levels which are
designations 2D3/2 and 2P1/2. Find the expected number of components in the
hyperfine structure of the corresponding spectral line.
Sol. For the state 2D3/2, we have
J = 3/2, I =3
The allowed values of the hyperfine structure quantum number F are
F = J+I, J+1 – 1, …., |J – I|
= 9/2, 7/2, 5/2, 3/2.
Thus, for this state there are four hyperfine structure levels.
377
For the state 2P1/2 , we have
J = ½ , I =3
So, F = 7/2 , 5/2.
This state has only 2 hyperfine structure levels.
E = 0 , 1.
Hence allowed transitions from the levels of one state to those of the other are:
9/2 7/2 , 7/27/2 , 7/25/2 , 5/27/2 , 5/25/2 and 3/25/2
(all are from 2D3/2 2P1/2)
So, total transitions are 6.
18.10
18.10Nuclear
NuclearSpin
Spinand
andHyperfine
HyperfineSplitting
Splitting
Isotope effect has its limitations. In many cases, this fails to explain the hyperfine
structure. Hyperfine components are often greater than the number of isotopes.
Similarly, some elements show hyperfine structure, even those are only isotope in
that element. For example bismuth exists as a single isotope, but shows six
hyperfine components in its line wavelength 4722 Å. Similarly, the number of
components of different lines is frequently quite different for one and the same
element.
In 1924, Pauli gave an explanation about hyperfine structure. According to him
when it assumed that the atomic nucleus possesses an intrinsic spin angular
momentum ⃗ and which is associated a magnetic dipole moment ⃗. Same as in the
case of spinning electron, the magnitude of the nuclear angular momentum is
ℎ
⃗ = ( + 1)
2
Where I is nuclear spin quantum number. It has different for different masses
number nuclei. It is also different for different isotopes of same element.
Since ⃗, ⃗ and ⃗ have quantized components along an axis in space. So the
component of ⃗ along the z-axis is
ℎ
=
2
where Ml = l, l – 1, l – 2, … , – l
378
Nuclear proton produces a magnetic moment ⃗ when it is in motion. This is
proportional to the angular momentum and which we can be written as
⃗= ⃗
2
Here e and mp are respectively the charge and mass of proton. The quantity gl is
called the ‘nuclear g factor’. The magnitude of the nuclear magnetic moment is
ℎ
= ( + 1)
2 2
ℎ
= ( + 1)
4
Here forms a natural unit for the measurement of nuclear magnetic moment
and is called the ‘nuclear magneton’µN. It is 1/1836 times the Bohr magneton
(because mass of proton is 1836 times the mass of electron). Thus,
= ( + 1)
The component of µl along z-axis is
=
where Ml = I, I – 1, I – 2, …, – I.
Since the maximum value of MI is I, the maximum observable component of µl is
gl IµN , and is commonly called the ‘nuclear magnetic moment’. It is roughly 1000
times smaller than electron magnetic moment.
Atomic Vector Model: Let us now construct the vector model with nuclear spin
taken into account. The total angular momentum of the whole atom is the sum of
three angular momenta: the electron orbital angular momentum ⃗, the electron spin
angular momentum ⃗ and the nuclear spin angular momentum ⃗. That is, the total
angular momentum is
⃗ = ⃗ + ⃗ + ⃗ = ⃗+ ⃗
As a result of interaction between electron orbit and spin, ⃗ and ⃗ precess rapidly
around their resultant ⃗. Further, the interaction between the nuclear magnetic
moment and the magnetic field produced by the orbital and spin motions of the
atomic electrons couples ⃗ with ⃗ and causes these vectors to precess around their
379
resultant ⃗ . This precession is however, about 1000 times slower than that of ⃗ and
⃗ about ⃗ because nuclear magnetic moment is so much smaller than electron
magnetic moment. Correspondingly the energy differences are very much smaller.
The hyperfine structure quantum number F can take the values:
F = J+I, J+I – 1, J+I– 2, … , |J – I|
having 2J + 1 values if I J or 2I+1 values if I J. This means that as a result of
I – J interaction, each fine structure J-level splits into 2J+1 (if I J) or 2I+1
( if I J) hyperfine structure levels, each characterized by an F value.
Interaction Energy: The ⃗ − ⃗ interaction energy can be shown to be given by
1
, = ′[ ( + 1) − ( + 1) − ( + 1)],
2
where A' is a constant. The various hyperfine structure levels of a given term of a
given atom have the same I and same J, but differ in F. Hence the separation
between two hyperfine structure levels can be obtained by substituting first F+1,
then F, in the above equation and taking the differences. This gives
1
′= ′[( + 1)( + 2) − ( + 1)]
2
′ = ′( + 1 )
Thus, the energy interval between consecutive hyperfine structure levels F and
F+1 is proportional to the larger of the F values (Lande's interval rule). The order
of hyperfine structure levels in some of the multiplets is normal (smallest F level
deepest) while in others it is inverted (largest level deepest).
The selection rule for F for electric dipole transitions is similar to that for J:
= 0, ±1 but F = 0 ←/→ F = 0
18.11
18.11Intensity
IntensityRatio
Ratioand
andDetermination
DeterminationofofNuclear
NuclearSpin
Spin
When the hyperfine structure components are observed due to the splitting of only
one of the terms, a measurement of the intensity ratio of the observed components
leads to the determination of nuclear spin. This is based on the ‘sum rule’,
according to which the sum of the intensities of the all the transitions starting from
or ending on the same level is proportional to the statistical weight 2F+1 of that
380
level. This situation arises in the hyperfine structure of the resonance lines of
sodium. In this case the ratio of the intensities of the two observed hyperfine
structure components is equal to the ratio of the weights (2F+1) of the hyperfine
structure levels of the term 2S½ ,where I is unknown. The F values of the two
hyperfine structure levels of the term 2S½ (J = ½) would be I + ½ and I – ½ .
Hence
1
2 +2 +1 +1
Intensity ratio = =
1
2 −2 +1
Thus, if intensity ratio is known, we can calculate nuclear spin I.
When I has been obtained, the g-factor and the magnetic moment of the nucleus
can be solved from the magnitude of the hyperfine structure splitting by using the
theoretical formulae.
When the hyperfine structure components are observed due to the splitting of both
the terms as in Bi line 4722 Å, then also an analysis of the hyperfine structure can
also lead to the determination of nuclear spin.
I = 9/2 F
5
1 1 3
, , 1
2 2 2
2 4
abc d ef
1 3 3 3
, , 4
2 2 2 3
2
5
6
Fig 22. Hyperfine structure for Bi
381
When all the hyperfine components are fully resolved (like Bi) then constant
wavenumber differences occur between pairs of components.
c–b=e–d
and d – b = e – c.
These differences correspond to level differences in the lower and the upper state
respectively, We arrange the wavenumbers of the hyperfine component in a square
array such that along each row and along each column they increase (or decrease)
regularly and the differences between them in two successive rows and successive
columns is constant. Then, all the components in any row correspond to the same
upper hyperfine structure level, while all those in any column correspond to the
same lower hyperfine structure level. This will enable us to construct hyperfine
structure energy for the upper and the lower states.
18.12
18.12Back
BackGoudsmit
GoudsmitEffect
EffectininHyperfine
HyperfineStructure
Structure
When we apply strong magnetic field ⃗ so the velocity of precession of ⃗ about
the field direction becomes greater than that of ⃗ and ⃗ about ⃗, an effect like
Pascen-Back effect will occurs in the hyperfine structure pattern. This effect is
called ‘Back-Goudsmit effect’. Since, weak coupling of ⃗ and ⃗, the Back-
Goudsmit effect occurs at fields much lower than those at which Paschen-Back
effect sets in fine-structure.
More precisely, magnetic field which is weak for fine structure is a strong field for
hyperfine structure. In this type of field the coupling between ⃗ and ⃗ breaks down
and each precesses independently around ⃗ with quantized components along the
field direction. These components take values ⃗ and respectively.
where
MJ = J, J – 1, J – 2, … , – J
and MI = I, I–1, I–2, …, –I
The total interaction energy of the atom consists of
(i) the energy of interaction between ⃗ and ⃗
(ii) the energy of interaction between ⃗ and ⃗.
382
By Larmor's theorem, the angular velocities of precession of ⃗ and ⃗ are given by
B times the corresponding ratios between the magnetic moment and angular
momentum. That is,
=
2
and
= =
2 2
18.13Self-Learning
18.13 Self-LearningExercise-
Exercise-IIII
Q.1 Find the expected number of components in the hyperfine structure of the
spectral line correspond to nuclear spin I = 3 and designations 2D3/2 and
2P1/2.
Q.2 What is the degeneracy of the fine-structure components of 3D3.
18.14
18.14Summary
Summary
Effect of magnetic effect on atomic structure can be measured with Zeeman Effect.
Similarly, Stark effect gives understanding of electric effect for same. It explains
the behavior of molecules due to presence of an external electric field. It is also an
application of quantum mechanical approaches. Even it can be observed in semi-
classical ground. Hyperfine splitting is very much useful in astrophysics, nuclear
technology and quantum computing.
18.15Glossary
18.15 Glossary
Multiplet : A group of spectral lines.
Dipole moment : Mathematical product of the separation of the ends of a dipole
and the magnitude of the charges (in simplest case).
Balmer series : Spectral emission lines of the hydrogen atom.
Electric field : A vector field that associates to each point in space the Coulomb
force.
Nuclear magneton : Magnetic dipole moments of heavy particles such as
nucleons and atomic nuclei.
383
18.16
18.16Answers
AnswerstotoSelf-Learning
Self-LearningExercises
Exercises
Answers to Self-Learning Exercise- I
Ans.1: The n = 3 level consists 9 states:
|3, 0, 0, |3, 1, –1, |3, 1, 0,
|3, 1, 1, |3, 2, –2, |3, 2, –1,
|3, 2, 0, |3, 2, 1 and |3, 2, 2
Here every state represents |n, l, m, n is principle quantum number, l is
azimuthal quantum number and m is magnetic quantum number after splitting.
Ans.2: First order Stark Effect splits the n = 3 into 5 sublevels with different
degeneracy:
Degeneracy States
1 |3, 0, 2
2 |3, –1, 2, |3, 1, 2
3 |3, –2, 1, |3, 0, 2, |3, 2, 2
2 |3, –1, 1, |3, 1, 1
1 |3, 0, 1
Ans.3: The interaction between the oscillating charge and the external electric field
gives rise to a term HP= qEX,
= + = − + +
(a) Let us take a variable change y = X + qE/m2
ℎ 1
= + −
8 2 2
This is Hamiltonian of a harmonic oscillator from which a constant,
q2E22/2m is subtracted. So, exact energy eigenvalue is:
1 ℎ
= + −
2 2 2
384
(b) Since, if we apply weak electric field, we can calculate terms
corresponding to HP as perturbation
First order correction is zero and second order correction is
( )
= −
2
Total energy = ground state energy + perturbed energy
1 ℎ
= + −
2 2 2
This agrees with previous result.
Answers to Self-Learning Exercise- II
Ans.1: For the state 2D3/2 , we have
J = 3/2, I =3.
Allowed hyperfine structure quantum number F are:
F = J + I, J + I – 1, … , | J – I |
For state 2P½ , we get
J = ½, I =3
So, F = 7/2, 5/2
Ans.2: J = 3, I = 3/2.
The allowed values of hyperfine structure quantum number F are
F = J + I, J + I – 1, … , | J – I |
9 7 5 3
= , , , .
2 2 2 2
Thus there are 4 hyperfine structure components whose designations which
are
, , ,
18.17
18.17Exercise
Exercise
Q.1 What do you understand about nuclear spin and hyperfine splitting ?
Q.2 What is Stark Effect ?
Q.3 Discuss weak field Stark effect.
385
Q.4 Discuss strong field Stark Effect.
Q.5 Explain transitions of Stark effect components in hydrogen.
Q.6 Explain a simple way to determine nuclear spin.
Q.7 How can we measure the isotopes in an element ?
Q.8 What is Back Goudsmit effect ?
Q.9 What is the difference between Goudsmit effect and Paschan back effect ?
Q.10 Give some areas which has application for hyperfine structure.
18.18
18.18Answers
AnswerstotoExercise
Exercise
Ans.1: See section 18.10
Ans.2: See section 18.1
Ans.3: See section 18.2
Ans.4: See section 18.3
Ans.5: See section 18.3 and 18.4
Ans.6: See section 18.6
Ans.7: See section 18.7
Ans.8: See section 18.12
Ans.9: See section 18.12
Ans.10: See section 18.14
References
Referencesand
andSuggested
SuggestedReadings
Readings
1. H.W. Kroto, Molecular Rotation Spectra, Dover, New York (published in
1992)
2. H. Friedrich, Theoretical Atomic Physics. Springer-Verlag, Berlin (published
in 1990)
3. The Modern Theories (1800-1950). American Institute of Physics
4. Harald A. Enge, Introduction to Nuclear Physics. Addison Wesley (published
in 1966)
5. Nouredine Zettili, Quantum Mechanics: Concepts and Applications
386
UNIT-1
UNIT-19
Plasma
Introduction to Molecular Spectra
Structure of the Unit
19.0 Objectives
19.1 Introduction
19.2 Introduction to Molecular Spectroscopy
19.3 Separation of Electronic and Nuclear Motion: The Born-Oppenheimer
Approximation
19.4 Types of Molecular Energy States and Associated Spectra
19.5 Types of Molecular Spectra (Characteristics of band spectra)
19.6 Regions of Molecular Spectrum
19.7 Signal-to-Noise Ratio and Resolving Power
19.8 Width of Spectral Line
19.9 Intensity of Spectral Line
9.10 Self Learning Exercise
19.11 Summary
19.12 Glossary
19.13 Exercise
References and Suggested Readings
19.0
19.0Objectives
Objectives
The objective of this chapter is to make familiar the readers with the basics of
molecular spectroscopy i.e. interaction of radiation with the molecules of matter.
The existence of various energy levels of molecules in the solids, the separation
between these energy levels and the regions of existence of spectra in the
electromagnetic spectrum will be presented. The basic idea regarding the features
of molecular spectra related to instrumentation will also be presented.
387
19.1
19.1Introduction
Introduction
In this chapter the basic features of molecular spectroscopy and the energy
levels of the molecules are explained. The origin of energy levels of the molecules
in the crystals, the separation between various energy levels and the regions of the
spectrum (Far IR, NIR and UV-Visible) accompanying the transition between
these energy levels are discussed. Some features of molecular spectra in view of
instrumentation like signal-to-noise ratio, width of spectral line, resolving power,
etc. are explained.
19.2
19.2Introduction
IntroductiontotoMolecular
MolecularSpectroscopy
Spectroscopy
The interaction of Electromagnetic radiations with matter is called as
spectroscopy. The electromagnetic radiations act as a probe to obtain the
information about the atoms and molecules which are very small enough to see.
The interaction of radiation with matter can influence the matter or/and radiations.
This interaction of radiation with matter provides the information about the matter
i.e. its constituents like atoms or molecules, binding between the atoms, structure
and shape of the molecules etc. The molecular spectra are different to as that of
atomic spectra. The atomic spectra contain discrete spectral lines and hence called
as line spectra. The molecular spectra are complicated as compared to atomic
spectra. These spectra contain a number of lines separated by small spacing
forming a band. Due to this reason the molecular spectra are called as band spectra.
The intensity of lines varies from one edge to another edge of a band.
Atomic Energy Levels
388
Diatomic Molecule
Molecular Energy Levels
389
19.3
19.3Separation
Separationof of
Electronic andand
Electronic Nuclear Motion
Nuclear : The: Born-
Motion The
Oppenheimer Approximation
Born-Oppenheimer Approximation
The energy levels in molecules are different as compared to an atom. In molecules
nuclear motion also contributes to energy levels (rotational and vibration levels).
The allowed energy levels can be obtained by solving the Schrodinger equation as:
Hφ=Eφ
In the molecules ,the nuclei and electrons are interacting. The electrons are very
light particles as compared to nuclei. Therefore the motion of electrons and nuclei
are considered to be separated to good approximation. This separation of electronic
and nuclear motions is called as Born-Oppenheimer approximation. So by using
this approximation the Schrodinger Equation can be solved in two steps:
1. The wave equation is solved for electronic motion by considering nuclei are to
fixed.
2. After this the wave equation is solved for the motion of nuclei and the eigen
values of electronic wave equation are considered to be part of potential
energy.
The Hamiltonian for a molecule consisting of j nuclei and i electrons is given by
m
h2 2
n
h2
H 2
j 2
i2 Vne Vee
j 1 8 m j i 1 8 m
Where first term of L.H.S. is the operator for kinetic energy for nuclei, second term
is the operator for kinetic energy operator for electrons, third term is potential
energy function for nuclear-nuclear interactions, fourth term is the potential energy
function for the nuclear-electron interaction and the last term is due to potential
energy function for electron-electron interactions.
By considering the nuclei in a fixed position, the kinetic energy of nuclei is
taken as zero and Vnn is treated as constant. So the Hamiltonian for the electron
will be
n
h2 2
H e i V ne V ee
i 1 8 2m
The Nuclear Hamiltonian is given by
390
m
h2
H n 2
2j Vnn
j 1 8 m j
So the total Hamiltonian is given by
H Hn He
Now according to Born-Oppenhiemer, the wave function of the molecule can be
written as product of electronic and nuclear wave functions
Let φ is the wavefunction of the molecule and φe and φn are the
wavefunctions of electrons and the nuclei so,
φ=φe φn
Let E is the total eigen value of the total eigen function then
H φ=E φ
H (φe φn)=E( φe φn)
h2 2 h2
[ 2
j 2
i2 ] e n (Vnn Vne Vee ) e n E e n
j 8 M j i 8 m
Using
2j e n e 2j n
i2 e n ni2 e
h2 2 h2
[ 2
1 2
22 V (r )] E
8 M 1 8 M 2
h2
( H e Ee ) [ 2 2j Ee Vnn ]
j 8 M j
h2 2 h2
e j n n
[ i2 Vne Vee ] e Vnn e n E e n
j 8 2 M j i 8 2
m
In the above equation
h2
H e e [ 2
i2 Vne Vee ] e
i 8 m
If the eigen values of the electronic wavefunction is Ee then
H e e E e
So,
391
h2
e 2j n Ee n e Vnn e n E e n
j 8 2 M j
( H n Ee ) n E n
e v r t
E Ee Ev Er Et
d 2 f 8 2 J ( J 1)h 2
[ E V ( r ) ]f 0
dr 2 h2 8 2 r 2
J ( J 1)h 2
V (r ) V (r )
8 2 r 2
1
R(r ) f (r )
r
h2
[ 2j Ee Vnn ] n E n
j 8 2 M j
( H n Ee ) n E n
In the above equation Ee is the eigen value of the electronic wavefunction and act
as part of potential energy for nuclear motion. So, the effective Hamiltonian for
molecular wavefunction is
h2
( H e Ee ) [ 2j Ee Vnn ]
j 8 2 M j
First the equation is solved for a given electronic state of the molecule for a range
of values of inter-nuclear co-ordinates. It will give values of φe and Ee as a
function of nuclear co-ordinates. After obtaining Ee, the above Schrodinger wave
function φn and eigen value É are determined. Different sets of wavefunction φn
and eigen value É are obtained for each electronic state of the molecule. Finally,
the total wavefunction φ=φnφe is determined.
19.4
19.4 Types
Types of
of Molecular
Molecular Energy
Energy States and associated
states and AssociatedSpectra
Spectra
Born-Oppenheimer approximation stated that motions of the electrons in a
molecule can be treated separately from those of nuclei and that the electronic
motion can be solved by assuming the nuclei to be fixed. The electronic energy Ee
and nuclear-nuclear interaction energy then act as an effective potential for the
motion of the nuclei.
392
The nuclear motion in a molecule is further divided into vibration, rotation,
and translational motions. In the approximation the electronic, vibration, rotation
and translation motions are considered to be independent. The Hamiltonian of
molecules is written as
H He Hv H r Ht
where
H e e Ee e
H v v Ev v
H r r Er r
H t t Et t
The total wavefunction is written as
e v r t
and the total energy is given by
E Ee Ev Er Et
For simplicity we here consider a diatomic molecule. The Schrodinger
wave equation for nuclear motion of the diatomic molecule is as
h2 2 h2
[ 2
1 2
22 V (r )] E
8 M 1 8 M 2
where V(r) is the effective potential energy contributed from the nucleus-
nucleus interaction and electronic energy state, is the eigen function and E is the
eigen value. The above equation can be transformed into polar co-ordinates. The
radial part of this equation is given by
1 d 2 dR 8 2 J ( J 1)h 2
( r ) [ E V ( r ) ]R 0
r 2 dr dr h2 8 2 r 2
where J is the total angular momentum of the molecule and J=0, 1, 2, 3, 4......
Let us now consider
1
R(r ) f (r )
r
Then the above equation get converted into
d 2 f 8 2 J ( J 1)h 2
[ E V ( r ) ]f 0
dr 2 h2 8 2 r 2
393
J ( J 1)h 2
V (r ) V (r )
Let 8 2 r 2
Here Ee is the eigen value of the electronic wavefunction, Vnn is the potential
J ( J 1)h 2
energy due to nucleus-nucleus interactions and the term is due to
8 2 r 2
centrifugal potential energy arising due to superposition of rotational motion on the
vibrations of particles. The variation of potential V(r) is as shown below
394
If the nuclear vibrations are small oscillations so V(r) can be expanded by Taylor’s
series as
V (r ) 1 2V (r )
V (r ) V (re ) (r re )[ ]r re (r re ) 2 [ 2 ]r re ......
r 2 r
If V(re)=0 and at r=re, V (r ) =0, so
r
1 2 2V (r )
V ( r ) = (r re ) [ ]r re
2 2r
The potential energy is a parabolic function near r=re for small displacement. The
molecule in this case can be treated as harmonic oscillation. Here r=re is the
equilibrium inter-nuclear separation and at this the potential energy is minimum.
If nuclear-nuclear interaction is ignored then V(r)min=Ee. When two atoms are
brought nearer to form a stable molecule, the electronic energy decreases rapidly
while the energy of repulsion increases. For certain inter-nuclear separation the
total potential energy is minimum i.e. for r-re, V(r)=Min. It is called as equilibrium
inter-nuclear position. The two nuclei vibrate about their equilibrium position
along the inter-nuclear axis and it also rotates about the centre of mass. So, we can
conclude now the following from the potential energy V(r):
1. The energy at minimum of V(r) is called as electronic energy Ee if the nuclei
are fixed.
2. The energy of nuclear vibrations about the nuclear position re under the
potential function V(r) is called as vibration energy Ev and is given by
quantum number v.
3. The energy of rotation of the molecule Er is given by quantum number J.
So the total energy of the molecule is given by
E Ee Ev Er
In terms of wavenumber
E Ee Ev Er
hc hc hc hc
or
v ve G (v) F(v,J)
where
395
ve = Electronic term
G(v) = Vibration term
F(v,J) = Rotation term
As a result a molecule has number of quantized electronic levels. The
transition between two electronic levels results in a radiations that fall in the UV-
Visible region. Within each electronic level a number of vibration energy levels
exist. The spacing between these levels decreases with increasing vibration
quantum number (v) . A transition between vibration levels results in the emission
of radiations that fall in the near Infra-red region. Also each vibration level is
associated with a number of rotational levels. The spacing between these levels
increases with increase in rotational quantum number. A transition between two
rotational levels gives rise to emission of radiations that fall in the far Infra-red
region.
Transitions In Molecular Energy Levels
A spectral line in each band arises due to change in the energies Ee, Ev and Er
E E
v
hc
396
Ee Ee Ev Ev Er Er
v
hc hc hc
v ve vv vr
Here ve vv vr .
So now summarize the following:
1. For a given band ve and vv are constant while vr changes from line to line. The
position in the band vv =0 is called as origin of band.
2. For a system of bands ve is constant while vv changes from band to band. The
position in the system vv =0 and vv =0 is called system origin.
3. The electronic band system lies in UV-Visible region.
4. The vibration-rotation band arises due to transition between two vibrational
levels of the same electronic state. The lines of the band result from the
transition between rotational levels of one vibrational level to the rotational
levels of other vibrational levels. Such band lies in near Infra-red region.
5. For a given electronic and vibrational level as same, the transition between
two rotational levels give rise to pure rotational bands. These lines fall in Far
Infra-red region.
19.5
19.5 Types
Types ofof Molecular Spectra (Characteristics
(Characteristics ofof Band
Band
Spectra)
Spectra)
The molecular spectra under low dispersion appear as continuous bands.
The intensities of a band decrease from one edge to other. With an instrument
having high resolving power band spectra are found to have internal structure as:
Each band is composed of large number of lines having very small
separations. There is a strong overlapping of the lines in higher wavelength
region i.e. near band head.
There exist a group of bands in a definite sequence.
The bands are very close to each other so forming a band system.
19.6
19.6Regions
RegionsofofMolecular
MolecularSpectrum
Spectrum
The molecules have electronic, vibrational and rotational levels. All these
levels are quantized. The transition between these energy levels due to absorption
or emission of energy will result in number of spectral lines in the spectrum of the
397
molecule. The interactions of molecules with electromagnetic radiations mainly
fall in following regions:
If the energy of the excited state is E and the ground state is E then the
frequency of the spectral line is as
E E
Hz.
h
E E
v cm-1
hc
1. UV-Visible or Electronic Spectra: The electronic transitions in a molecule
require energy of the order of 5-10 eV. The wavenumber and wavelength
corresponding to 5 eV is
5 1.6 1019
v
6.6 1034 3 108
4.04 106 m 1
1 1
v 4.04 106
25 106 cm 2500 Ao
This lies in the UV or short wavelength visible region. In each electronic state
there are a number of possible vibrational states. Also in a vibrational state
there is a set of rotational states.
2. Near Infra-red Spectra or Vibrational-rotational spectra: The vibrational levels
are separated from each other by an energy gap of order 0.1 eV. The
wavenumber and wavelength corresponding to 0.1 eV is
0.1 1.6 10 19
v
6.6 1034 3 108
8 104 m 1
1 1
v 8 104
12.5 106 m 125000 Ao
These transitions fall in the near Infra-red region. The vibrational transitions
are always accompanied by change in rotational levels. So such spectra are
called as vibrational-rotational spectra.
398
3. Far Infra-red Spectra or Pure rotational Spectra: The vibrational levels are
separated from each other by an energy gap of order 0.005 eV. The
wavenumber and wavelength corresponding to 0.005 eV is
0.005 1.6 1019
v 4040m 1
6.6 1034 3 108
1 1
2.47 104 m 2470000 Ao
v 4040
19.7
19.7Signal-to-Noise
Signal-to-NoiseRatio
Ratioand
andResolving
ResolvingPower
Power
1. Signal-to-Noise Ratio: In spectrometers some electronics amplification
devices are used to magnify the signal produced by the detector, the recorded
spectrum has a background of random fluctuations caused by spurious
electronic signals produced by the source or detector or may be generated by
amplifying device. These fluctuations are called as “noise”. In order that a
spectral line should appear as such and can easily be distinguished from noise
the intensity of spectral line should be at least three or four times that of noise
399
signal. By using computer averaging technique the signal-to-noise ratio can be
improved.
2. Resolving Power: The resolving power is related to ability of the spectrometer
to distinguish between different spectral lines situated close to each other. By
decreasing the slit width of the spectrometer the resolving power can be
improved. The sensitive detector can also enhance the resolving power.
19.8
19.8Width
WidthofofSpectral
SpectralLine
Line
When we record the absorption or emission spectrum then we find broader
spectral lines instead of sharp lines. The design of the spectrometer can
improve the resolving power but the width of the spectral line of any atomic or
molecular spectrum cannot be reduced below an inherent width of that line.
This width arises due to non-sharp single energy levels of the atoms or
molecules. There is a width of energy of the state involves in the transition. The
following factors contribute to the width of a spectral line:
1. Collision Broadening: In the liquid and gases phases the atoms and molecules
are in continuous motion and they collide with each other. Due to these
collisions a change in the electronic, vibrational and rotational levels take place
causing the broadening of the spectral lines. In case of solids the spectra are
sharper as compared to liquid or gases phases.
2. Doppler Broadening: Due to motion of molecules in liquid and gases phases
there is a Doppler shift in the spectral line. Due to this shift the lines get broader.
400
3. Natural Broadening: In the atoms or molecules which are at rest the
energy levels are not sharp as stated by Heisenberg uncertainty principle.
According to this principle if the system exists in an energy state for a time
Δt seconds then the energy of that state will be uncertain by an amount ΔE.
h
E.t 1034 Js
2
Here h is the Planck’s constant. The lower energy state is sharp while upper state is
not sharp. So the spectral line has finite width as
h
E
2.t
1
2.t
19.9
19.9Intensity
IntensityofofSpectral
SpectralLine
Line
The intensity of a spectral line depend the following factors:
1. Transition Probability: The transition probability is related to fact that the
transition between two states is allowed or forbidden i.e. the transition
probability is non-zero or zero. The probability of transition is related to
derivation of selection rules for the transition between two levels.
2. Population of two states: The intensity of a spectral line depends upon the
population of that state from which the transition takes place.
Suppose there are N molecules distributed over two states of energies as E1 and
E2 such that E2 > E1, then from statistical mechanics
E1
kT
N1 Ne
401
E2
kT
N 2 Ne
( E2 E1 ) E
N2 kT
e e kT
N1
3. Path Length of Sample: The sample absorbs the radiations which are incident
on it. If the path of the sample is increased then more and more radiation will be
absorbed. The absorbance of a sample is given by
I0
A log( ) cl
I
c = Concentration
ε = Molecular absorption coefficient.
l = Path length
9.10
9.10Self
SelfLearning
LearningExercise
Exercise
Q.1 Why molecular spectra are called as band spectra.
Q.2 Write the total wavefunction for a molecule and explain it.
Q.3 Write the order of wavelength of each region of molecular spectra.
Q.4 Explain Signal-to-Noise ratio.
Q.5 Explain the intensity of a spectral line. On which factors the intensity of the
line depends?
19.11
19.11Summary
Summary
The unit has introduced the concepts of molecular energy levels. How these energy
levels arise due to mutual interaction between the atoms of the molecule. The total
potential energy function of the molecule is calculated and then the Schrodinger
wave equation is solved by using Born- Oppenheimer approximation. The
molecule has three types of energy levels i.e. electronic, vibrational and rotational
energy levels. The transitions between these levels give rise to molecular spectra
i.e. band spectra. In the later section of unit order of energies involving the
transitions between these levels and the corresponding regions of their fall are
discussed. Finally there is a discussion on the width of spectral line and their origin
as well how the spectrometer will be able to record the spectral line precisely.
402
19.12
19.12Glossary
Glossary
Band : Group of energy levels separated by small energy gap
Spectra : Plural of spectrum
Spectrometer : Instrument to record the spectrum.
Hamiltonian : Total energy operator in quantum mechanics.
Eigen value : Value of a physical quantity in quantum mechanics
Centrifugal : Towards the centre
Interaction: Influencing by a force
Width : Interval
Noise : Unwanted signal
Resolve : Keep separation
Spurious: Duplicate
19.13
19.13Exercise
Exercise
Q.1 What is the difference between atomic and molecular spectrum.
Q.2 What is origin of band spectra of molecules ?
Q.3 Explain the Born-Oppenheimer approximation.
Q.4 Write the total Hamiltonian for a Molecule.
Q.5 Write the effective potential energy function for a molecule and explain it.
Q.6 Write the various regions of molecular spectra.
Q.7 What is the order of energy of quanta of various regions of molecular
spectrum.
Q.8 Write the order of frequencies of different region of molecular spectra.
Q.9 Draw the energy level diagram of molecular levels.
Q.10 Write the characteristics of molecular spectra.
Q.11 How the Signal-to-Noise can be improved ?
Q.12 What is the resolving power of spectrometer ? How the resolving power can
be improved ?
403
Q.13 Explain the width of a spectral line. Explain the various factors on which the
width of line depends upon ?
References
Referencesand
andSuggested
SuggestedReadings
Readings
1. Colin N. Banwell and Elaine M. McCash: Molecular Spectroscopy, Tata
Mcgraw-Hill Education Private Limited, New Delhi, 1994.
2. J. M. Holias: Modern Spectroscopy , John Wiley & Sons, England, 1987.
3. S.L. Gupta, V. Kumar and R.C. Sharma: Elements of Spectroscopy, Pragati
Prakashan, Meerut, 1990.
4. Raj Kumar: Atomic & Molecular Spectra: LASER, Kedar Nath Ram Nath,
Meerut, 2007.
404
UNIT-20
Microwave Spectroscopy
Structure of the Unit
20.0 Objectives
20.1 Introduction
20.2 Salient features of Rotational Spectra
20.3 Molecular Requirement for Rotational Spectra
20.4 The Molecule as Rigid Rotator: Explanation of Rotational Spectra
20.5 The Intensities of Spectral Lines
20.6 Diatomic Molecule as a Non-Rigid Rotator
20.7 Isotopic Effect
20.8 Rotational Spectra of Polyatomic Molecule
20.9 Rotational spectra of Symmetric Top Molecules
20.10 Illustrative Examples
20.11 Self Learning Exercise
20.12 Summary
20.13 Bibliography
20.14 Exercise
References and Suggested Readings
20.0
20.0Objectives
Objectives
This unit is designed to let readers with the knowledge of pure rotational
spectra of molecules. The basic features of the molecular spectra, energy of
rotational levels of a diatomic molecule as rigid and non-rigid rotator and the
transition between these energy states will be explained. The various types of
polyatomic molecules and the rotational spectra of some simple polyatomic
molecule will also be discussed.
405
20.1
20.1Introduction
Introduction
The pure rotational spectra are shown by those molecules which have
permanent electric dipole moment. The salient features of the pure rotational
spectra, rotational spectra of a rigid and non-rigid diatomic molecule, intensity of
spectral lines and selection rules for transition between rotational levels are
discussed. The various types of polyatomic molecules and the spectra of symmetric
top molecule are explained.
20.2
20.2 Salient
SalientFeatures
FeaturesofofRotational
RotationalSpectra
Spectra
1. The spectral lines which are observed in far Infra-red region in the wavelength
range greater than 200µm are due to transitions between rotational energy
levels of the molecule.
2. The change in these transitions is of the order of 0.0005 eV.
3. Only those molecules which have permanent electric dipole moment can give
rise to rotational spectra. It is the basic requirement to show rotational spectra
by the molecules.
4. The homo-nuclear molecules like H2 , O2 , N2 , etc. do not show rotational
spectra.
5. Only the hetero-nuclear molecules like HF, HCl, HBr, etc. show the rotational
spectra.
6. The rotational spectra are observed in absorption mode.
7. From the spectral lines of rotational spectra the moment of inertia of the
molecule and inter-nuclear distance can be calculated.
8. The polar molecules interact with electric field of Infra-red radiations to
absorb energy and will show absorption spectra.
9. The rotational spectral lines are observed at equidistance on wavenumber
scale.
20.3
20.3 Molecular
MolecularRequirement
Requirementfor
forRotational
RotationalSpectra
Spectra
The basic requirement for the emission or absorption of radiations by
transitions between rotational energy states is that the molecule must have a
permanent electric dipole moment. This can be explained on the basis of theory of
406
classical electrodynamics. According to this theory a rotating molecule can lead to
emission of radiations if the dipole moment of hetero-nuclear molecule changes.
All hetero-nuclear molecules have a permanent electric dipole moment. During the
rotation of the molecule this dipole moment changes periodically in a particular
direction with frequency of rotation rot . of the molecule, so as per classical theory
of electrodynamics it will emit the radiation of frequency rot . . The homo-nuclear
molecules have no electric dipole moment and hence there is no emission of
radiations.
Similar to emission the Infra-red radiations can be absorbed by rotating
molecules if they have permanent electric dipole moment is present. The molecules
interact with oscillating electric field of the incident radiation to absorb rotation
energy and produce absorption lines.
Suppose the electric field of the electromagnetic wave at any instant of time
pushes the positive ions in the upward direction and negative ions in the downward
direction. As a result the molecule will rotate faster. If frequency of radiations
coincides with that of molecular rotation ,then in the next half cycle, the molecule
will rotate faster as compared to previous half cycle. As a result the molecule will
be excited to higher rotational state. So the absorption spectrum is only observed
when the molecule has electric dipole moment.
2020.4.4The
The Molecule
Molecule as
as Rigid Rotator :: Explanation
Explanation ofof
Rotational
RotationalSpectra
Spectra
Let us consider a hetero-nuclear diatomic molecule having masses of two
atoms as m1 and m2. The bond between two atoms is rigid i.e. not flexible. Let r be
distance between two atoms which remain constant. Let r1 and r2 be the distance
atoms m1 and m2 from the centre of mass C of the molecule. The molecule is
rotating about an axis passing through the centre of mass and perpendicular to
inter-nuclear axis. From the property of centre of mass as
m1r1 m2 r2
r r1 r2
r1 r r2
m1 ( r r2 ) m2 r2
407
m1r ( m1 m2 )r2
m1r
r2
(m1 m2 )
m2 r
Similarly r1
(m1 m2 )
The moment of inertia of the molecule about the axis of rotation is given by
I m1r12 m2 r22
m1m22 r 2 m2 m12 r 2
I
(m1 m2 )2 (m1 m2 )2
m1m2 m1m2
I 2
[m2 m1 ]r 2 r 2 r 2
(m1 m2 ) (m1 m2 )
m1m2
where
(m1 m2 )
µ is called as reduced mass of the molecule.
In order to find the energy of rotation of molecule we have to solve the
Schrodinger’s wave equation as
2 8 2
2 ( E V ) 0
h
In terms of spherical polar co-ordinates the Schrodinger wave equation is
1 2 1 1 2 8 2
( r ) ( Sin ) 2 E 0
r2 r r r 2 Sin r 2 Sin 2 2 h
Since r is fixed so the differentiation with respect to r are taken as zero
1 1 2 8 2 I
( Sin ) 2 E 0 ,
Sin Sin 2 2 h
where I r 2 ,I is the moment of inertia of the molecule.
408
Let us now separate the variables and as
Let ( , ) ( ). ( )
1 ( ) 1 2 ( ) 8 2 I
( Sin ) ( ) ( ) E( ). ( ) 0
Sin Sin 2 2 h2
Dividing by ( ). ( )
1 ( ) 1 1 2 ( ) 1 8 2 I
( Sin ) E0
Sin ( ) Sin 2 2 ( ) h2
Multiplying the equation by Sin2θ
Sin ( ) 1 2 ( ) 8 2 I
(Sin ) 2
2 E.Sin2 0
( ) ( ) h
Sin ( ) 8 2 I 1 2 ( )
(Sin ) 2 E.Sin 2
( ) h ( ) 2
1 2 ( )
Let us consider M2
( ) 2
2 ( )
2
M 2 ( )
2 ( ) (A)
M 2 ( ) 0
2
and
Sin ( ) 8 2 I
(Sin ) 2 E.Sin 2 M 2
( ) h
( )
On multiplying by to above equation
Sin 2
1 ( ) 8 2 I ( )
( Sin ) 2 E.( ) M 2
Sin h Sin 2
1 ( ) 8 2 I M2
(Sin ) [ 2 E ]( ) 0 (B)
Sin h Sin 2
The solution of the equation (A) is
M ( ) AeiM
where, M 0, 1, 2, 3.......etc.
409
In order to solve equation (B), we consider the following
Let x Cos and P ( x ) ( )
( ) P x P
Then Sin 2 1 x 2 and Sin
x x
d d
Let us treat (....) Sin (....) as an operator, so the equation (B) become
d d
1 d dP ( x) 8 2 IE M2
[ Sin { Sin Sin( )}] [ 2 ]P ( x ) 0
Sin dx dx h Sin 2
d 2 dP ( x ) 8 2 IE M2
[ (1 x ) ][ 2 ]P ( x ) 0
dx dx h (1 x 2 )
d 2 P ( x) dP ( x) 8 2 IE M2
(1 x 2 ) 2 x [ ]P ( x ) 0 (C)
dx 2 dx h2 (1 x 2 )
This equation is identical to associated Legendre’s differential equation if
8 2 IE h 2 J ( J 1)
we replace by J(J+1) or E , here J is a positive integer. So the
h2 8 2 I
solution of the above (C) equation will be
M M
I , M ( ) N .PJ ( x ) N .PJ (Cos )
M has values as, M=J, J-1, J-2, J-3, ---------, -J+1, -J.
So, the complete wave function is given
( , ) N .PJM (Cos ) A.eiM
The rotational energy states are given by
h 2 J ( J 1)
EJ
8 2 I
h 2 J ( J 1)
where is the eigen value of the square of the angular momentum as
4 2
h 2 J ( J 1)
Lˆ2 , J=0, 1, 2, 3, 4, ..., etc.
4 2
Mh
and are the eigen values of Z-components of the angular momentum as
2
Mh
LˆZ , M 0, 1, 2, 3,......, etc.
2
The angular frequency of rotation is given by
410
L h
rot J ( J 1)
I 2 I
and the frequency of rotation is given by
h
rot J ( J 1)
2 4 2 I
Rotational Spectrum: The energy of a rigid rotator is given by
J ( J 1)h 2
EJ , where J=0, 1, 2, 3, 4, ..., etc.
8 2 I
Corresponding to different values of J ,there will be different energy states of
rotations of a diatomic molecule. In term of wavenumber
E h
F (J ) 2 J ( J 1)
hc 8 Ic
F ( J ) BJ ( J 1)
h
where B , B is called as rotational constant.
8 2 Ic
If J=0, 1, 2, 3, 4, 5, ......., etc., then, F(J)=0, 2B, 6B, 12B, 20B, ....., etc.
When the transitions take place between an upper level and lower level of
rotational levels, then the wave number of absorbed radiation will be
411
v F ( J ) F ( J )
v BJ ( J 1) BJ ( J 1) (D)
The selection rule for the transitions to take place is
J 1
If J J 1 , then from equation (D) we have
v B ( J 1)( J 2) BJ ( J 1) , v 2 B ( J 1)
From the above we see that the absorption spectrum of a rigid rotator contains a
series of equidistant lines having separation 2B.
20.5
20.5 The
TheIntensities
IntensitiesofofSpectral
SpectralLines
Lines
The spectral lines are observed in the rotational spectra of molecule for
ΔJ=±1. The probability of these transitions is same irrespective of levels involved
in the transitions. But the intensity of the spectral lines emerging due to transitions
between pair levels having different values of J is not same. This is related to the
different number of molecules in a state ,therefore the number of molecules
undergoing transitions from different levels will be different. The intensity of
spectral line is proportional to number of molecule in the initial state. The number
of molecules in a state is given by
EJ BhcJ ( J 1)
N J N 0 e kT N 0 e , kT
Here T is the temperature and K is the Boltzmann constant.
412
As the value of J and B increases NJ decreases. The population of the level is
proportional to degeneracy of a rotational level i.e. for a given value of J there will
be (2J+1) sublevels of same energy. So the population of a level is given by
EJ BhcJ ( J 1)
N J (2 J 1) N 0e kT (2 J 1) N 0e kT
20.6
20.6 Diatomic
DiatomicMolecule
MoleculeasasaaNon-Rigid
Non-RigidRotator
Rotator
From the experimental investigation of the spectral lines of rotational
spectra it is found that the spectral lines are equally spaced but the separation
between lines decreases on wavenumber scale as the value of rotational quantum
number J increases. From the calculation of rotational constant it is found that the
bond length increases with increase in J , so the rigidity of the rotator is under
question. We may here conclude that with increase in J value the increase in bond
length is due to elastic nature of the bond up to some extent. The centrifugal force
tends to increase the bond length at higher value of J. As a result of change in bond
length due to stretching or compressing the molecule periodically, it is assumed the
molecules may have vibrational energy. If the motion is simple harmonic the force
constant is given by
k
k 4 2 v 2 c 2 or v2 2 2
4 c
By considering the effect of non-rigidity of the bond the rotational energy levels
are as
h2 h4
E J ( J 1) J 2 ( J 1)2
8 2 I 32 4 I 2 r 2 k
E
F (J ) BJ ( J 1) DJ 2 ( J 1) 2
hc
h2 h3 4B 3
where B and D and D
8 2 Ic 32 4 I 2 r 2 kc v2
Here D is called as centrifugal distortion constant. So the energy of rotational
energy level of high J values is lowered as shown above. The wavenumber of the
transition between two levels
v F (J 1) F(J) B[(J 1)(J 2) J(J 1)] D[(J 1) 2 (J 2) 2 J 2 ( J 1) 2 ]
v F (J 1) F(J) 2 B(J 1) 4 D(J 1) 2
413
The selection rule for transition is J 1 . Due to centrifugal distortions the
spectral lines are not equally spaced particularly at higher value of J.
20.7
20.7Isotopic
IsotopicEffect
Effect
If any atom in the molecule is replaced by its isotope then the reduced mass
of the molecule µ changes. Due to this change the moment of inertia changes but
the inter-nuclear distance remains the same.
Before the isotopic exchange in the molecule
m1m2
, and I r 2
(m1 m2 )
If m1 is exchanged by its isotopic mass m then
m1m2
, and I r 2
(m1 m2 )
Due to isotopic exchange the rotational energy values and the frequency separation
of successive lines in the rotational spectrum changes. If m >m1 then >µ and
I >I. So rotational constant B changes as
414
h2 h2
As, B , so due to isotopic exchange it become B , so B´<B, and
8 2 Ic 8 2 I c
F ( J ) B J ( J 1) , F´(J)<F(J). So the wave number after the isotopic exchange is
given by
v 2 B ( J 1) , so v < v
So the separation of levels for heavier isotopes will be smaller as compared to
original mass. If m1 <m1, then v > v i.e. for lighter isotopic exchange, the
separation between levels is higher as compared to original mass.
So we conclude that the spectral lines will be closer on isotopic substitution if
m1 >m1 and wider if m1 <m1 as compared to m1. The isotopic effect increases with
increase in value of J.
20.8
20.8Rotational
RotationalSpectra
SpectraofofPolyatomic
PolyatomicMolecule
Molecule
In order to understand the spectra of polyatomic molecule ,we must be
aware of the principal moment of inertia, angular momentum and kinetic energy of
the polyatomic molecule.
1. Principal Moment of Inertia : Suppose there are N atoms in a polyatomic
molecule. Then there will be 3N degrees of freedom, out of these three belong to
rotation of whole molecule about three mutually perpendicular axes. The moment
of inertia of N atoms about any axis of rotation is written as
I m1r12 m2 r2 2 m3 r32 m4 r4 2 ........ mN rN 2
Now there exists one direction of three mutually perpendicular axis for which
corresponding moment of inertia are maximum or minimum. The axis along these
directions pass through centre of mass. The maximum and minimum values are
called as principal moment of inertia. They are Ia , Ib and Ic with I a I b I c .
2. Angular Momentum: The angular momentum is given by
L I
In terms of inertial tensor
Lx I xx I xy I xz x
Ly I yx I yy I yz y
L I I zy I zz z
z zx
In terms of principal moment of inertia the above can be written as
415
La I a 0 0 a
L 0 0
b Ib b
L 0 I c
c 0 c
3. Kinetic Energy in terms of Principal Moment of Inertia: The kinetic
energy of the molecule in terms of principal moment of inertia is given by
1
K [ I aa2 I bb2 I cc2 ]
2
L2 L2 L2
K [ a b c ]
2 Ia 2I b 2 I c
4. Types of Molecules on the basis of Principal Moment of inertia: On the
basis of principal moment of inertia of the molecule the molecules are classified as
(a) Asymmetric Tops: Three moment of inertia are different i.e.
Ia Ib I c
(b) Symmetric Tops: Two moments of inertia are equal i.e.
I a I b I c , for oblate symmetric top
I a Ib I c , for prolate symmetric top
(c) Spherical Tops: Three moments of inertia are equal i.e.
Ia Ib I c I
(d) Linear or Diatomic Molecule: Two moment of inertia are equal and one is
zero i.e.
I a 0, I b I c
20.9
20.9 Rotational
Rotationalspectra
spectraofofSymmetric
SymmetricTop
TopMolecules
Molecules
In the symmetric molecule two moments of inertia are equal and one is
different. The examples of such molecules are CH3Cl and NH3. The rotational
energy of the molecule is given by
L2a L2 L2
Er b c
2I a 2Ib 2I c
For a linear molecule it is assumed that the total angular momentum is quantized as
h
L J ( J 1) , where J = 0, 1, 2, 3, 4, ...., etc.
2
The rotational energy of such molecules depend upon two quantum numbers J and
K because J may not be directed perpendicular to top axis (Ia axis or unique
416
principal axis). K is the component of vector J along top axis and K is also
quantized.
Kh
La , K 0, 1, 2, 3,...., etc.
2
L2 L2a L2b L2c
h2 2 h
2
L2 L2a L2b L2c J ( J 1) K
4 2 4 2
So the rotational energy is given by
For Prolate type Molecule
K 2 h 2 J ( J 1)h 2 K 2 h 2
Er 2 , as Ib = Ic
8 2 I a 8 2 I b 8 I b
J ( J 1)h 2 h2 h2
Er ( )K 2
8 2 Ib 8 2 I a 8 2 I b
The term value is given by
Er J ( J 1)h h h
F (J , K ) 2
( 2 2 )K 2
hc 8 I b c 8 I a c 8 I b c
F ( J , K ) BJ ( J 1) ( A B ) K 2
h h
Where B 2
,A 2
8 Ib c 8 I a c
The quantum numbers J and K can take the values as
J = 0, 1, 2, 3, 4, ......, etc.
K = 0, ±1, ±2, ±3, ±4, ....etc.
So all values having K>0 are double degenerate.
The selection rules for transitions are as
ΔJ = 0, ±1 and ΔK = 0
For absorption spectrum
ΔJ = +1 and ΔK = 0
For oblate type of the molecule
Ia = Ib < Ic, so
417
F ( J , K ) BJ ( J 1) (B C ) K 2
h
where C , and (B-C) is positive since Ib < Ic
8 2 I c c
The wave number of the pure rotational absorption spectral transition
v F ( J 1, K ) F ( J , K )
v [ B ( J 1)( J 2) ( A B ) K 2 ] [ BJ ( J 1) ( A B ) K 2 ]
-1
v 2 B( J 1) cm
20.10
20.10Illustrative
IllustrativeExamples
Examples
Example1. The wavenumber of first line in the rotation spectrum of CO is
3.84235 cm-1. Calculate the rotational constant, moment of inertia and bond length
of the molecule. (Given mass of C=19.92168×10-27 kg and mass of
O = 26.5636×10-27 kg)
Sol. Given that v01 3.84235cm 1 2 B
418
So B = 1.92118 cm-1
The moment of inertia of Co molecule is
h 6.626 1034
I 1.457 1046 kgm 2
8 2 Bc 8 (3.14)2 3 108 1.92118 10 2
The reduced mass of the molecule is related to bond length as
mC mO 19.92168 1027 26.56136 1027
27
11.38365 1027 kg
mC mO (19.92168 26.56136) 10
I 1.45695 1046
As I r 2 , so r 1.131 1010 m
11.38365 1027
Example 2 Wave number of J =0 to 1 transition in HCl molecule found at
20.68 cm-1. Calculate the wavelength for the transition J = 14 to J = 15.
Sol. The wave number of the transition from J = J to J =J+1 is
v 2 B( J 1)
For J = 0 to J = 1
v 2B
As v= 20.68 cm-1
So 2B = 20.68 cm-1
B = 10.34 cm-1
So the wavenumber for the transition J= 14 to J = 15 is
v 2 B( J 1) , here J = 14
v 2 B (14 1) 2 10.34 15 310.2cm 1
So the wavelength of the transition is
1 1
3.2 103 cm 32 m
v 310.2
Example 3 In the rotational spectra of C12O16 the first absorption line (J = 0 to
J = 1) is observed at 1.153×1011 cycles/s and for CnO16 it is observed at
1.102×1011 cycles/s. Find the value of n for Carbon isotope. (Given that mass of
C12 = 12 a.m.u. and mass of O16 = 16 a.m.u.).
Sol. Before isotopic exchange the rotational constant is
419
h2
B , and v 2 B( J 1)
8 2 Ic
After isotopic exchange the rotational constant is
h2
B , and v 2 B ( J 1)
8 2 I c
v B I (12 16) ( n 16)
v B I 12 16 n 16
1.153 1011 28 (n 16)
11
1.102 10 (12 16) (n 16)
1.153 7 n
1.102 3 n 16
3.459 n
7.714 n 16
(7.714 3.459) n 3.459 16
3.459 16 55.344
n 13.0068
4.255 4.255
So the isotope of Carbon is C13.
20.11
20.11Self
SelfLearning
LearningExercise
Exercise
Q.1 Why rotational is not observed for homo-nuclear molecules ?
Q.2 Give the examples of polar molecules.
Q.3 Discuss the pure rotational spectra of a rigid rotator. Show that the spectral
lines are equally spaced on wavenumber scale.
Q.4 What is a symmetric molecule ? Explain oblate and prolate type of a
symmetric molecule.
20.12
20.12Summary
Summary
The aim of this unit is to study the pure rotational spectra of the diatomic
and symmetric top molecules. The pure rotational spectra of the molecule lie in far
Infra-red region of electromagnetic region. The pure rotational spectra are shown
by hetero-nuclear molecules. These molecules have permanent electric dipole
moment. The homo-nuclear molecules do not show the pure rotational spectra
because they do not have permanent electric dipole moment. The mechanism of
420
interaction of dipolar molecules with the electric field of electromagnetic field
leading to change in the rotational state was discussed. The pure rotational
spectrum of diatomic molecule have been discussed in detail. The energy levels
and selection rules for transitions have been explained. The spectral lines are found
to equally spaced on wave number scale. The effect of non-rigidity and isotopic
exchange has been also discussed for a diatomic molecule. The shift in the spectral
due to these effects has been presented. The introduction about the rotational
spectra of polyatomic molecules has been also introduced and the rotational
spectrum of symmetric top molecules has been discussed in detail. At last some
problems related to the content of the units have been solved.
20.13
20.13Glossary
Glossary
Homo-nuclear : Same type of nucleus
Hetero-nuclear : Different type of nucleus
Polar : Having positive and negative charge
Oscillating : Periodically varying
Rigid : Hard to change
Flexible : Easy to change
Centrifugal : Away from centre
Distortion : Defects
Successive : Consecutives
Degenerate : Same energy
20.14Exercise
20.14 Exercise
Q.1 What is requirement for a molecule to show rotational spectrum ?
Q.2 How the polar molecules interact with electromagnetic radiations ?
Q.3 Write region of pure rotational spectrum and order of quanta of energy for
transition between two levels.
Q.4 What is the order of wavelength of pure rotational spectra ?
Q.5 Write the Schrodinger’s wave equation for a rigid rotator.
Q.6 Write the formula for population of a rotational level and its degeneracy.
421
Q.7 Discuss the dependence of intensity of spectral lines on the population of a
rotational level.
Q.8 Write the formula for energy of rotation of a rigid rotator and the selection
rules for transition between two levels.
Q.9 Discuss the effect of non-rigidity on the pure rotational spectra of a diatomic
molecule.
Q.10 Discuss the effect of isotopic exchange on the pure rotational spectra of a
diatomic molecule.
Q.11 Discuss the various types of polyatomic molecules on the basis of principal
moment of inertia.
Q.12 Discuss the rotational spectrum of a symmetric top molecule.
References
Referencesand
andSuggested
SuggestedReadings
Readings
1. Colin N. Banwell and Elaine M. McCash: Molecular Spectroscopy, Tata
Mcgraw-Hill Education Private Limited, New Delhi, 1994.
2. J. M. Holias: Modern Spectroscopy , John Wiley & Sons, England, 1987.
3. S.L. Gupta, V. Kumar and R.C. Sharma: Elements of Spectroscopy, Pragati
Prakashan, Meerut, 1990.
4. Raj Kumar: Atomic & Molecular Spectra: LASER, Kedar Nath Ram Nath,
Meerut, 2007.
422
UNIT-21
InfraredInfrared
Spectroscopy : Part : Part-I
Spectroscopy
Structure of the Unit
21.0 Objectives
21.1 Introduction
21.2 Salient features of Vibrational-Rotational Spectra
21.3 Vibrating Diatomic Molecule as Harmonic Oscillator
21.4 Vibrating Molecule as Anharmonic Oscillator
21.5 Vibrational Frequency and Force Constant for Anharmonic Oscillator
21.6 Isotopic Effect in Vibrational Spectra
21.7 Molecule as Vibrating Rotator
21.8 Breakdown of Born-Oppenhemier Approximation: The Interaction of
Rotations and Vibrations
21.9 Illustrative Examples
21.10 Self Learning Exercise
21.11 Summary
21.12 Glossary
21.13 Exercise
References and Suggested Readings
21.0
21.0Objectives
Objectives
This chapter is aimed to provide knowledge to the readers about the population of
vibrational energy levels of molecules. The different modes of vibrations of
polyatomic molecules will be discussed. The instrumentation for recording the IR
spectra of the molecules will be explained.
21.1
21.1Introduction
Introduction
The vibrational energy levels of the molecules are quantized. The population of
423
these energy levels at any temperature will be discussed. The normal coordinates
of vibrations and various modes of vibration of polyatomic molecules are
explained with examples. The instrumentation required to record the IR spectra of
the molecules is discussed i.e. FTIR spectrometer.
21.2
21.2 Salient
Salientfeatures
featuresofofVibrational-Rotational
Vibrational-RotationalSpectra
Spectra
The salient features of vibrational-rotational spectra are as follows:
1. The vibrational-rotational spectra fall in the Near-Infra-Red (NIR) region of
electromagnetic spectrum (1µm-100µm).
2. During the vibrational transitions between vibrational levels of molecule there
is no change in the electronic state.
3. The vibrational transitions are always are accompanied by rotational
transitions.
4. The vibrational-rotational spectra observed in absorption mode.
5. The vibrational-rotational spectra are observed for those molecules which have
permanent electric dipole moments e.g. HCl, HBr, HI, HF, H2O etc.
6. When the molecule vibrates, then the inter-nuclear distance changes. So, the
dipole moment of the molecule also changes. The electric dipole moment of
molecule oscillates and emits the radiation of frequency which lies in the
Near-Infra-Red region.
7. The oscillating electric dipole moment also interacts with the incident
radiations and absorbs the radiations of frequency of Near-Infra-Red region.
8. The vibrational-rotational spectra of diatomic molecules consist of an intense
band called as fundamental band surrounded by weak bands called as
overtones.
21.3
21.3Vibrating
VibratingDiatomic
DiatomicMolecule
MoleculeasasHarmonic
HarmonicOscillator
Oscillator
Let us consider a diatomic molecule which is vibrating and whose
vibrations are treated as simple harmonic. Let re be the equilibrium length of the
bond between two atoms of the molecule. At any instant of time during the
vibration the bond length is r. The equation of motion the atoms in the molecules
are as
d 2 r1
m1 2 k (r re ) (A)
dt
424
d 2 r2
m2 k (r re ) (B)
dt 2
where m1 and m2 be masses of the two atoms, r1 and r2 be the position of two atoms
from the centre of mass and k is the force constant.
From the properties of centre of mass we have
m1r1 m2 r2
r r1 r2
r1 r r2
m1 (r r2 ) m2 r2
m1r (m1 m2 )r2
m1r
r2
( m1 m2 )
m2 r
and r1
( m1 m2 )
So by substituting the values of r1 and r2 in equation (A) and (B) we get the
equation as
m1 m2 d 2 r
( ) k (r re ) (C)
m1 m2 dt 2
Since, re is constant so we can replace r by (r - re) in equation (C)
m1 m2 d 2 (r re )
( ) k (r re ) (D)
m1 m2 dt 2
Let r re x and m1 m2 , so the equation (D) now become
m1 m2
d 2x
2 kx
dt
425
d 2x k
x0
dt 2
d2x k
2
2 x 0 , where 2
dt
The frequency of vibration is given by
1 k
Hz.
2
In terms of wave numbers
1 k 1 1
v cm
2 c
The energy of the vibrational energy levels is quantized. The allowed energies for
the diatomic molecule can be determined by solving the Schrodinger’s wave
1 2
equation considering the potential to be harmonic as V kx0 . The energy of
2
levels of diatomic molecule is given by the following equation
1 1
Ev [v ]h [v ]hcv
2 2
Here v is the vibrational quantum number which can take values as v = 0, 1, 2, 3,
...., etc.
In terms of term value the above equation is written as
426
1
G (v) [v ]v , for v =0, 1, 2, 3, 4, ...etc the values of G(v) are as
2
v v v v
G ( v) ,3 ,5 , 7 ,.....etc.
2 2 2 2
So we observe a series of levels which are quantized and equispaced.
Suppose a transition takes place from higher vibrational energy state having
quantum number v to lower vibrational state having quantum number v ,then the
frequency of radiation emitted given by
( Ev Ev )
Hz
h
In term of wavelength
( Ev Ev )
G (v) G(v) cm 1
hc
The selection rule for transition is Δv = ±1.
21.4
21.4 Vibrating
VibratingMolecule
MoleculeasasAnharmonic
AnharmonicOscillator
Oscillator
For a diatomic molecule as purely harmonic oscillator the change in
vibrational quantum number is Δv = ±1 ,so there is one band for each mode of
vibration. But experimentally there is strong band with one or two overtones or
harmonics. The harmonics correspond to the frequencies that are resulted due to
change in vibrational quantum number Δv = ±2, ±3,… etc. Thus the overtones
correspond to transitions involving the change in vibrational quantum number
Δv>1. Thus the dipole moment of the molecule is not linear with respect to inter-
nuclear distance, implying the presence of anharmonicity in the molecular
vibrations. The overtones are not observed exactly at 2v ,3v ,.. but at lower value
side. It indicates that the vibrational energy levels are not equispaced but converges
slowly as the vibrational quantum number increases. Due to presence of
anharmonicity ,the potential energy curve is not strictly parabolic but its shape
changes at higher values of quantum number v. The potential energy in this case is
given by as
1 2V (r ) 2 1 3V ( r )
V (r ) ( 2
) r re ( r re ) ( 3
) r re ( r re )3 ....
2 r 6 r
V (r ) f (r re )2 g (r re )3
427
Where g<<f. So the real molecules do not obey Hook’s law, there is anharmonicity
present in their vibrations. The potential energy curve for such oscillators is as
shown as below and by considering the above potential energy the Schrodinger
equation is solved.
The allowed vibrational levels are given by following equation
1 1 1
E (v) (v )h (v ) 2 h x (v )3 h y ......
2 2 2
Here x and y are the anharmonicity constants.
In terms of term values the above equation is written as
1 1 1
G (v ) (v )v (v ) 2 vx (v )3 vy ......
2 2 2
The quantity v is the line spacing of energy levels in terms of wavenumbers if the
potential energy is purely parabolic, vx is the anharmonicity constant whose value
is much smaller than v and is always positive. So the energy levels are not at
equispaced as observed from above equation. As the value of vibrational quantum
number v increases separations between levels decrease. The selection rules for
transitions between vibrational levels after considering the anharmonicity are as
428
Δv = ±1, ±2, ±3, .........., etc.
These transitions are classified as fundamental band corresponding to transition
v = 1 to v = 0 , first overtones or second harmonics for v = 2 to v = 0, and second
overtone or third harmonics for v = 3 to v = 0, etc.
Suppose a transition takes place from an upper vibration state v to lower state v
then the frequency of radiation is given by
( Ev Ev)
v Hz
h
In terms of wave number
( Ev Ev)
vv G (v) G (v)
hc
vv (v v)v {v(v 1) v(v 1)}xv
Since vibrational quantum number is always is zero so v = 0 and v = v , so the
wavenumber of fundamental band overtones are
v1 (1 2 x)v Fundamental band.
v2 (1 3x)2v First overtone.
v3 (1 4 x)3v Second overtone.
21.5
21.5 Vibrational
Vibrational Frequency
Frequency and Force Constant
Constant for
for
Anharmonic
AnharmonicOscillator
Oscillator
The vibrational frequency of harmonic oscillator is given by
1 k
2
where k is force constant and µ is the reduced mass. The separation between the
levels is constant and is equal to v in terms of wavenumber. In case of anharmonic
oscillator the above formula holds for small amplitude of vibrations. The
vibrational frequency of anharmonic oscillator in state v is given by
G 1 G 1
v v
2 2
cGv c
2
1
c[{G (v 1) G (v)} {G (v ) G (v 1)]
2
429
1
c[G (v 1) G (v 1)]
2
As we know that
1 1
G (v) v (v ) vx(v ) 2
2 2
1 3 3 1 1
So, c[{v (v ) vx(v ) 2 } {v (v ) vx(v ) 2 }]
2 2 2 2 2
1 3 1 3 1
c[{v (v v } vx{(v )2 (v )2 }]
2 2 2 2 2
1
c[2v vx(4v 2)]
2
c[v vx(2v 1)]
So as value of v increases ,the frequency of vibration decreases. From the
vibrational frequency of small amplitude vibration ,we have
1 k
cv
2
So the force constant is given by
k 4 2 c 2v 2
21.6
21.6 Isotopic
IsotopicEffect
EffectininVibrational
VibrationalSpectra
Spectra
The isotopic forms of the molecule have different reduced masses ,but the
force constant is same. From the value of force constant k 4 2 c 2v 2 , it is
observed that the equilibrium vibrational wavenumber will be different for
different isotopic form. Let v1 and v2 are the equilibrium wavenumbers for two
isotopic forms having reduced masses 1 and 2 . The from the force constant we
have
v2 1
, or v2 v1 (A)
v1 2
The anharmonicity constant is proportional to equilibrium constant so
x2 x1 (B)
So the wavenumber of the centre of any band involving lower vibrational level
v = 0 is
430
vv 0 v[1 (v 1) x1 ]v (C)
So by using equations (A) and (B) in (C) we
v
1 v 0 v[1 (v 1) x1 ]v
v
2 v 0 v[ (v 1) x1 2 ]v
The above equations represent the wavenumbers of the isotopic forms of same
molecule. The wavenumber difference of the centers of the two isotopic bands
called as isotopic shifts, vi .
vi (1 ){1 (v 1)(1 ) x1}v1
The isotopic shift for fundamental band, first overtone and second overtone are as
Fundamental Band v = 1 to v = 0
vi (1) (1 ){1 2(1 ) x1}v1
First Overtone v = 2 to v = 0
vi (2) (1 ){1 3(1 ) x1}2v1
Second Overtone v = 3 to v = 0
vi (3) (1 ){1 4(1 ) x1}3v1
The isotopic shift depends upon the factor (1 ) . The shift increases with increase
in (1 ) . If ρ>1, isotopic shift v is towards lower wavenumber and for ρ<1 the
shift is towards higher wavenumber side.
21.7
21.7 Molecule
MoleculeasasVibrating
VibratingRotator
Rotator
We have considered the vibrations and rotations of a diatomic molecule
independently up to now. But a vibrating molecule is always associated with
rotational motion so we have to consider the combined vibrational and rotational
motion of the molecule. Let us discuss this combined motion under situations.
I. Molecule as Rigid Rotator and Harmonic Oscillator
The Near Infra-red spectra of the molecules consist of bands which composed of
close lines arranged in a particular manner. This fine structure suggests that during
the vibrational transition the rotational state of the molecule also changes. The
molecule can be treated as vibrating rotator. Suppose the vibrations and rotations
431
of molecules take place independently i.e. there is no interaction between two
motions. The total energy of the molecule in this case can be written as
Evr Evib Erot
If the molecule is rigid rotator and harmonic oscillator ,then
Evr {G(v) F ( J )}ch
1 h2
Evr (v )hcv 2 J ( J 1)
2 8 I
Suppose a transition takes place from vibrational level v to v level along with
transition from rotational level J to level J . Then the change in energy
accompanies the transitions is
h2
Evr Evr Evr (v v)hcv [ J ( J 1) J ( J 1)]
8 2 I
The wavenumber of radiation arising due to the transition is
Evr Evr h h
vvr (v v)v B[ J ( J 1) J ( J 1)] ,where B 2
2 2
hc 8 Ic 8 r c
432
II. Diatomic Molecule as Non-rigid and Anharmonic Oscillator
If the diatomic molecule is not rigid rotator and there is anharmonicity is present in
the vibrations ,then the energy of the molecule is given by
Evr {G(v) F ( J )}ch
1 1
Evr ch[(v )v x (v )2 v ... BJ ( J 1) DJ ( J 2 1) 2 ...]
2 2
If we neglect the small centrifugal distortions ,then we take D = 0 and others then
the energy of the molecule in this case as
1 1
Evr ch[(v )v x(v ) 2 v BJ ( J 1)]
2 2
The selection rules for combined vibrational and rotational transition are as
v 1, 2, etc. J 1
433
Let us consider two vibrational state designated by v = 0 and v = 1. The rotational
states in v = 0 are denoted by J and in the state v = 1 are denoted by J . For the
transition from v = 0 to v = 1 the wave number of the radiation
Er,v 0 Er,v1
vvr
hc
3 9 3 1
vvr {BJ ( J 1) v xv } {BJ ( J 1) v xv }
2 4 2 4
vvr v (1 2 x) B( J J )( J J 1) v0 B( J J )( J J 1)
where v0 v (1 2 x) , it is the wave number of pure vibrational transitions
( J J 0 ).
v0 is called as wave number of the band origin.
Now let us consider
R Branch: J 1, i.e. ( J J ) 1 v (R) v0 2B( J 1), J 0,1, 2,....
P Branch J 1, i.e. ( J J ) 1 v (P) v0 2BJ , J 1, 2,....
In General vvr v0 2Bn , where n 1, 2, 3....etc. , n 0
So the vibrational-rotational spectra of diatomic molecule consist of numbers of
lines at a separation of 2B cm-1 around the centre of band.
21.8
21.8 Breakdown
Breakdownof ofBorn-Oppenhemier
Born-Oppenhemier Approximation: The
Approximation:
Interaction of Rotations
The Interaction and Vibrations
of Rotations and Vibrations
If we do not consider the interaction between vibrational and rotational
energies ,then the R and P branch lines are equidistant. But in actual practice the
separation between the lines of one branch decreases (R branch) and of the other
branch (P branch) increases. This is resulted due to interaction between vibrational
and rotational motion of the molecule.
When a molecule vibrates ,then the bond length changes which cause the
change in moment of inertia I and rotational constant B of the molecule. This is
called as interaction between two motions. As the vibrational quantum number v
increases ,the amplitude of vibrations increases ,hence the value of rotational
constant decreases due to increase in average bond length. The dependence of
rotational constant on vibrational quantum number can be expressed as
434
1
Bv Be (v ) ......
2
h h
where Bv and Be
8 2 I v c 8 2 I ec
Here Iv is the moment of inertia of molecule in vth vibrational state, Ie is the
moment of inertia in equilibrium state and α is a small positive integer of the order
of 0.02Be to 0.05Be. In the same way the non-rigidity constant of the molecule in
the vth state is given by
1
Dv De (v ) ......
2
Dv is the no-rigidity constant in vth state, De is non-rigidity constant in equilibrium
constant and β is constant as compared to De. So the rotational energy is given by
Er Bv J ( J 1)hc Dv J 2 ( J 1) 2 hc ...
Figure : Ideal Vibrational-Rotational Spectra
The total energy of the molecule after considering the interaction between
the vibrational and rotational motion is
1 1
Evr (v )hcv (v ) 2 hcxv .... Bv J ( J 1)hc Dv J 2 ( J 1) 2 hc ..
2 2
The wavenumber of the lines of P and R branches are
P Branch: v ( P) v0 ( Bv Bv) J ( Bv Bv) J 2 4 Dv J 3
R Branch: v ( R) v0 ( Bv Bv) J ( Bv Bv) J 2 4 Dv J 3
435
Here J = 0, 1, 2, 3, .........etc. and v0 is the wavenumber of the centre of band which
is given as
v0 (1 2 x)v , v 1 v 0
If we neglect the non-rigidity constant Dv ,then
P Branch: v ( P) v0 ( Bv Bv)m ( Bv Bv)m 2 , m = -1, -2, -3, ....
R Branch: v ( R) v0 ( Bv Bv)m ( Bv Bv)m 2 , m= +1, +2, +3, .....
Figure: Real Vibrational-Rotational Spectra (Fine Structure)
So we Conclude the following from the above theory
1. As the vibrational energy increases ,the average inter-nuclear distance
increases so the rotational constant Bv is smaller in the upper state than lower
state. So Bv Bv , means band head appears in R branch on high wavenumber
side of the origin. Such a band is said to be degraded towards the red. So the
vibrational-rotational spectra bands are degraded to red only.
2. The wavelength separation of successive lines in the P and Q branches are as
v ( P) 2Bv ( Bv Bv)2 J ...
v ( R) 2Bv ( Bv Bv)2 J ...
3. For both P and R branches Bv Bv , so the separation between the lines of R
branch decreases with increase in J values where as the separation between
lines of P branch increases with increase in J.
436
21.9
21.9Illustrative
IllustrativeExamples
Examples
Example1 The value of v and vx are 1580.36 cm-1 and 12.073 cm-1 respectively
for the ground state of molecular oxygen. Calculate the zero-point energy.
(1eV = 8068 cm-1 ).
Sol. The vibrational energy of the diatomic molecule is given by
1 1
G (v) v (v ) vx(v ) 2
2 2
For zero point energy v = 0 so
1 1 1 1
G (0) v vx ,
G (0) 1580.36 12.073 790.18 3.02
2 4 2 4
-1 787.16
G (0) 787.16 cm , G (0) 0.097eV
8068
Example 2 The force constant of the bond in CO molecule is 190 N/m and its
reduced mass is 1.15 1026 kg . Calculate the frequency of vibration and spacing
between the vibrational levels.
Sol. The frequency of vibration of the molecule is given by
1 k 1 190
2 2 3.14 1.15 1026
2.0467 1013Hz
The separation between the two energy levels
E Ev 1 Ev h
E Ev 1 Ev 6.63 10 34 2.0467 1013
E 6.63 10 34 2.0467 1013 13.5696 1021 J
13.5696 10 21
E eV
1.6 10 19
E 8.481102 eV
Example 3 HCl molecule absorbs wavelength 3.5 micrometer due to vibrational
transitions. Find the force constant for HCl molecule.
Sol. The frequency of vibrations is given by
1 k
2
437
k 4 2 2
Here mH 1.0087 a.m.u. and mCl 35.453 a.m.u.
So the reduced mass of the molecule is given by
mH mCl 1.0087 35.453
0.98 a.m.u.
(mH mCl ) (1.0087 35.453)
0.98 1.67 1027kg.
The frequency of vibration can also be written as
c 3 108
6
8.571 1013 Hz.
3.5 10
So the force constant is now given by
k 4 (3.14) 2 (8.5711013 ) 2 1.63 1027
k 472.24 N/m
Example 4 The fundamental band of a diatomic molecule is centered around
2145 cm-1 and first overtone at 4260 cm-1. Find v and vx .
Sol. The frequency of fundamental and first overtones are given by
v1 (1 2 x)v Fundamental band.
v2 (1 3x)2v First overtone.
v1 (1 2 x)
So,
v2 (1 3 x) 2
2v1 6v1 x v2 2v2 x
(2v2 6v1 ) x v2 2v1
(v2 2v1 ) (4260 4290) 30
x
(2v2 6v1 ) (8520 12870) 4350
x 0.0069
As 2v1 v2 2vx
(2v1 v2 ) 4290 4260
vx 15 cm-1
2 2
15 15
v 2174 cm-1
x 0.0069
438
21.10
21.10Self
SelfLearning
LearningExercise
Exercise
Q.1 What is the order of energy difference between vibrational levels of a
molecule ?
Q.2 Discuss the anharmonicity present in molecular vibrations.
Q.3 Discuss the effect of isotopic exchange on the vibrational spectra of a
diatomic molecule.
Q.4 Discuss the fine structure of the vibrational-rotational spectra.
21.11Summary
21.11 Summary
The aim of this unit is to study the vibrational-rotational spectra of the
diatomic molecules. First of all the pure vibrational motion of the molecule is
considered and the energies levels are determined. After this effect of
anharmonicity present in the molecule has been discussed. Due to anharmonic
effect the presence of fundamental band, first overtones and second overtones were
discussed. Effect of the isotopic exchange on the spectra has been also discussed.
After considering the pure vibrational motion the rotational motion of the molecule
is also considered. The two motions first treated as non-interacting and the total
energy of the molecule has been calculated. The combined vibrational and
rotational motion provides the presence different branches in the molecular spectra.
Different cases were considered regarding the rigidity and non-rigidity of the bond
as harmonic and anharmonic effect in the vibrations. At last the fine structure of
the vibrational-rotational spectra have been discussed. The fine spectra are related
to interaction of vibrational and rotational motion. The effect has been discussed
in terms of separation between the lines of different branches.
21.12
21.12Glossary
Glossary
Homo-nuclear : Same type of nucleus
Hetero-nuclear : Different type of nucleus
Polar : Having +ive and –ive charge
Oscillating : Periodically varying
Rigid : Hard to change
Flexible : Easy to change
439
Distortion : Defects
Converge : Terminating
Degraded : Ending
21.13Exercise
21.13 Exercise
Q.1 Write the order of frequency and wavelength of NIR spectra.
Q.2 How the polar molecules interact with electromagnetic radiations ?
Q.3 Give the examples of polar molecules.
Q.4 Write the selection rules for transitions between the vibrational levels.
Q.5 Are the vibrations of a diatomic molecules are pure harmonic ?
Q.6 Discuss the effect of anharmonicity on the vibrational spectra.
Q.7 Discuss the fundamental band and various overtones in vibrational spectra.
Q.8 Discuss the effect of isotopic exchange on the fundamental and on the
overtones of the vibrational spectra.
Q.9 Write the formula for calculation of force constant of bond in a diatomic
molecule.
Q.10 Discuss the Vibrational-Rotational spectra of diatomic molecules. Discuss
the various branches of the spectra.
Q.11 Write the selection rules for transitions in vibrational-rotational spectra.
Q.12 Discuss the effect of non-rigidity and anharmonicity on the NIR spectra.
Referencesand
References andSuggested
SuggestedReadings
Readings
1. Colin N. Banwell and Elaine M. McCash: Molecular Spectroscopy, Tata
Mcgraw-Hill Education Private Limited, New Delhi, 1994.
2. J. M. Holias: Modern Spectroscopy , John Wiley & Sons, England, 1987.
3. S.L. Gupta, V. Kumar and R.C. Sharma: Elements of Spectroscopy, Pragati
Prakashan, Meerut, 1990.
4. Raj Kumar: Atomic & Molecular Spectra: LASER, Kedar Nath Ram Nath,
Meerut, 2007.
5. G.M. Barrow, Introduction to Molecular Spectroscopy, McGraw Hill, London,
1961.
440
UNIT-22
Infrared Spectroscopy : Part-II
Structure of the Unit
22.0 Objectives
22.1 Introduction
22.2 Thermal Distribution of Vibrational and Rotational Levels
22.3 Vibrational Spectra of Polyatomic Molecules
22.4 Fundamental Vibrations and their Symmetry
22.5 Analysis by Infra-red Techniques
22.5.1 Skeletal Vibrations
22.5.2 Group Frequencies
22.6 Fourier-Transform Infrared Spectrometers
22.6.1 Michelson Interferometers
22.6.2 Sources and Detectors
22.6.3 Fourier-Transformation
22.6.4 Moving Mirrors
22.6.5 Signal-Averaging
22.6.6 Computers
22.6.7 Spectra
22.7 Self Learning Exercise
22.8 Summary
22.9 Glossary
22.10 Exercise
References and Suggested Readings
441
22.0
22.0Objectives
Objectives
This chapter is aimed to provide knowledge to the readers about the population of
vibrational energy levels of molecules. The different modes of vibrations of
polyatomic molecules will be discussed. The instrumentation for recording the IR
spectra of the molecules will be explained.
22.1
22.1Introduction
Introduction
The vibrational energy levels of the molecules are quantized. The
population of these energy levels at any temperature will be discussed. The normal
coordinates of vibrations and various modes of vibration of polyatomic molecules
are explained with examples. The instrumentation required to record the IR spectra
of the molecules is discussed i.e. FTIR spectrometer.
22.2
22.2 Thermal
Thermal Distribution
Distribution of Vibrational
Vibrational and
and Rotational
Rotational
Levels
Levels
Vibrational Levels : According to Maxwell-Boltzmann distribution law the
number of molecules in the vth state, Nv , relative to lowest state, N0, is given by
G0 ( v ) hc
Nv N0e kT
, k is the Boltzmann constant and T is the
temperature. G0(v) is the energy term value of the transition from vth state to zero
state.
1 1
G0 (v) G (v) G(0) , G (v ) v (v ) vx(v ) 2
2 2
At room temperature the population of higher vibrational levels is very small as
compared to lowest level v = 0. As the temperature increases the population of
higher vibrational levels increases as shown in the graph 22.1.
Rotational Levels : The relative population of various rotational levels
corresponding to a vibrational level is of different nature. A rotational state having
rotational quantum number J is (2J+1) fold degenerate. The probability of a
molecule to be in each degenerate state is equal. Let the molecules are in the
lowest vibrational state v = 0, Nv=0 , be the number of molecules in this state. These
molecules are distributed in various rotational states. The number of molecules in a
rotational state of a given vibrational state is as
442
F ( J ) hc
N v 0
NJ (2 J 1)e kT
Zr
where Zr is the rotational partition function which is given by
F ( J ) hc
Z r (2 J 1)e kT
J 0
BJ ( J 1) hc
Z r (2 J 1)e kT
J 0
BJ ( J 1) hc
kT
kT
Z r (2 J 1)e dJ
0
hcB
Figure:22.1 Population of Rotational levels
BJ ( J 1) hc
NJ hcB
So (2 J 1)e kT
Nv 0 kT
NJ
We see here that as the value of J increases, the value of first increases and
N v 0
then decreases. The value of J for which the population is maximum is calculated
BJ ( J 1) hc
d NJ d hcB
as ( ) ( (2 J 1)e kT ) 0
dJ N v 0 dJ kT
443
kT 1
J max
2 Bhc 2
Thus, the value of J at which the population is maximum, increases with decrease
in B and increase in temperature. As the temperature of the molecular gas increases
,then the following effects are observed.
1. The extension of band takes place along both sides i.e. along P branch and
R branch.
2. The intensity maxima in both branches moves farther from v0 .
3. The intensity maximum is found for higher value of J.
4. The height of intensity maxima decreases.
5. The inequality between the intensity of two branches becomes less marked.
22.3
22.3 Vibrational
VibrationalSpectra
SpectraofofPolyatomic
PolyatomicMolecules
Molecules
A polyatomic molecule having N atoms have 3N degrees of freedom i.e. 3N
co-ordinates are required to specify the positions of all nuclei. Out of these 3N
degree of freedoms 3 are related to translational motion, 3(non linear molecule) or
2(linear molecule) are related to rotational motion and remaining 3N-6(non linear
molecule) or 3N-5 (linear molecule) are related to vibrational motion. There will
be 3N-6 or 3N-5 energy levels corresponding to these vibrations. So in the
spectrum of the molecules having n atoms there will be 3N-6 (non linear molecule)
or 3N-5(linear molecule) absorption bands.
Normal Co-ordinates and Normal Modes of Vibrations
For the analysis of spectra shown by polyatomic molecules ,the study of
modes of vibrations is essential. Let us consider a linear diatomic molecule having
3N-6 degree of freedoms denoted by m and generalized coordinates q1, q2, q3, ...qm,
representing the equilibrium state of each nucleus. The potential energy of can be
expanded by Taylor’s series in terms of these coordinates, i.e.
V 1 2V
V Veq { }eq qi { }eq qi q j ......
i qi 2 i , j qi q j
If the equilibrium potential energy is taken as reference and chosen to be zero then
1 2V V
V {
2 i , j qi q j
}eq qi q j , because { }eq 0
qi
in equilibrium position.
444
Let us consider that
1 2V 1
bij { }eq , then V bi , j qi q j
2 i , j qi q j 2 i, j
The kinetic energy is given by
1 . .
K i , j i q j , where the coefficients are given by
2 i, j
m q
rk rk
mi , j m j ,i mk ( )( ) mi , j (q1 , q2 , q3 ,....qm )
k qi q j
mij
mi , j (mi , j )eq ( )ql ......
k ql
If we consider only the first term of the series ,then the kinetic energy is written as
1 . .
K i, j i q j
2 i, j
a q , where aij (mij )eq
The Lagrangian of the system is given by
1 . .
L K V ij i q j bij qi q j )
2 i, j
( a q
The Lagrangian’s equation of motion are
m
d L L
[ dt ( .
)
qi
]0
i 1 qi
d 1 . 1
[ aij q j bij q j 0
dt 2 j 2 j
..
aij q j bij q j 0
j j
(A)
It represents a set of m equations (i = 1, 2, 3, ....., m). The general solution of such
equation is as
q j Aj Sin(t ) (B)
where Aj is the amplitude and ω is the angular frequency which is given by
2
By substituting from (B) in equation (A) we get
445
(b
j
ij aij ) A j 0, i 1, 2,3...m
which gives a set of m simultaneous linear homogeneous equations in A’s and if
A’s are not all to be zero then
(b
j
ij aij ) 0
b a .... b1n ann
11 11
or b21 a21 .... b2 n ann 0
.... .... ....
b a .... bnn ann
n1 n1
This equation is an equation of mth degree giving m values of λ in terms of a’s and
b’s. These values of λ’s or ω2 are the normal frequency of vibrations of a
polyatomic molecule.
We now consider the normal coordinates, such that each of them execute
only one single frequency oscillations. Let us now transform the equations in qi’s
to normal coordinates Qj’s as
i
qi Cij Q j or q CQ
j 1
where (q) and (Q) are single column matrices. In order to write the equation
of motion in terms of normal coordinates ,we have to find first the kinetic energy
and potential energy and the Lagrangian in terms of Q’s. The potential energy is
given by
1
V bij qi q j
2 i, j
, which is a quadratic in q. Any quadratic expression is of the form
can be written as
q12 q22 2 q1q2
which can be written as
q1 T
( q1 , q2 ) X UX
q2
q1
where X
q2
446
U
X T (q1 , q2 )
Now we can write V as
1 T
V q bq
2
1
V C T QT bCQ
2
1
V QT C T bCQ
2
1
V QT Q
2
where C T bC
So the potential energy can be written as
1
V k2Qk2
2 k
1 1
T aij qi q j q T q
2 i, j 2
1 1 1
T Q T C T CQ Q T Q Q k2
2 2 2
where CT C 1
Therefore Lagrangian will be
1
V k2Qk2
2 k
1 1
T aij qi q j q T q
2 i, j 2
1 1 1
T Q T C T CQ Q T Q Q k2
2 2 2 k
CTC 1
1 1
L T V Q k2 k2Qk2
2 k 2 k
m
d L L
[ dt ( Q
k 1
)(
Qk
)] 0
k
447
m
[Q
k 1
k k2Qk ] 0
2 Q 0
Q m m m
Qm Am cos mt Bm sin mt
which when used with
m
d L L
[ dt ( Q
k 1
)(
Qk
)] 0
k
[Q
k 1
k k2Qk ] 0
or 2Q 0
Q 1 1 1
2Q 0
Q 2 2 2
2Q 0
Q 3 3 3
....................
...................
2 Q 0
Q m m m
Corresponding to Q1 the frequency is ω1 , for Q2 it is ω2 , and so on. The Q’s are
called as normal coordinates. The solutions to above equations are as
Q1 A1 cos 1t B1 sin 1t
Q2 A2 cos 2t B2 sin 2t
Q3 A3 cos 3t B3 sin 3t
.....................................
.....................................
Qm Am cos mt Bm sin mt
Here ω1, ω2, ω3, ......ωm are called as normal frequencies.
22.4
22.4 Fundamental
FundamentalVibrations
Vibrationsand
andtheir
theirSymmetry
Symmetry
Let us consider a molecule containing N atoms. The position of each atom
can be specified by three coordinates i.e. x, y, and z coordinates. So there will be
3N coordinates i.e. molecule has 3N degree of freedom. Now the molecule is free
to move in three dimensional space as a whole without change of shape. The
448
translational motion uses three degree of freedom leaving 3N-3 as remaining. Also
a non-linear molecule has three degree of freedom due to rotations . So the
molecule is left with 3N-6 degree of freedom. The only other motion allowed to
molecule is the internal vibrations, so a non-linear molecule will have 3N-6 degree
of freedom due to internal vibrations. If the molecule is linear, then there will be
3N-5 degree of freedom due to internal vibrations. In both types of molecules there
are N atoms, so there will be N-1 bonds (acyclic molecules) between the atoms.
There will be N-1 vibrations are of bond stretching type motions and 2N-5 (non-
linear) or 2N-4 (linear) are of bending type motions.
In case of diatomic molecule N=2 and 3N-5=1, so there is only one
fundamental vibration. In case of tri-atomic non-linear molecule like H2O, there are
3N-6=3 allowed vibrational modes called as normal modes. Theses modes of
vibrations are shown as below.
Figure 22.2 Vibrations of Water Molecule
Figure 22.3 Vibrations of Carbon Dioxide Molecule
449
Each vibrational motion is labeled as symmetric or antisymmetric. If we rotate the
vibrating molecule by 1800 such that vibration is quite unchanged in character then
it is called as symmetric vibrations. However if the rotation produces a vibration
which is in antiphase with the original ,then such motion is called as antisymmetric
stretching mode. The vibrations of water molecule and carbon dioxide molecule
are shown in figure.
22.5
22.5 Analysis
AnalysisbybyInfrared
InfraredTechniques
Techniques
A complex molecule has 3N-6 or 3N-5 normal modes of vibrations. Each
normal mode involves some displacement of all or nearly all the atoms in the
molecule, but in some of the modes ,all atoms may undergo approximately the
same displacement and in others the displacement of a small group of atoms may
be much more vigorous than the remainder. Thus we may divide the normal modes
into two groups as skeletal vibrations and characteristics group vibrations. The
skeletal vibrations involve many of the atoms to same extent and the characteristic
vibrations involve only a small portion of the molecule while others remain
stationary.
22.5.1 Skeletal Vibrations
For organic molecules these fall in the range 1400-700 cm-1 and arise from
linear or branched chain structure in the molecule. Thus each such group gives rise
to several Skeletal modes of vibrations and hence several absorptions bands in the
infra-red.
It is not possible to assign particular bands to specific vibrational mode, but the
observed band is highly typical of a molecular structure under examination.
Further a change in the chain or ring in the form of substitution results in a marked
change in the pattern of absorption band. These bands are treated as fingerprint of a
particular molecular structure.
450
Figure:22.4 The adsorption bands at 1605 cm-1 and 1517 cm-1 were
characteristic of phenyl ring skeletal vibrations of lignin macromolecules.
22.5.2 Group Frequencies
The group frequencies are usually independent of the structure of the
molecule as whole and fall in the regions well above and well below that of
skeletal modes. The group frequencies of some functional groups are given in table
below.
451
Table:22.1 Vibrational Frequencies of Functional Groups (cm-1)
Shift in the characteristic frequencies occurs due to two major factors. Firstly the
shift may arise due to interactions between the different molecules. Secondly, the
shift in the frequencies is also due physical state of molecules. The more
condensed phase gives lower frequencies particularly in case of polar molecules. In
non polar molecules there is no shift in symmetric vibrations but a smaller shift in
others.
22.6
22.6 Fourier-Transform
Fourier-TransformInfrared
InfraredSpectrometers
Spectrometers
Fourier-transform infrared (FTIR) spectroscopy is based on the idea of the
interference of radiation between two beams to yield an interferogram. The latter is
a signal produced as a function of the change of path length between the two
beams. The two domains of distance and frequency are inter-convertible by the
mathematical method of Fourier-transformation. The basic components of an FTIR
spectrometer are shown schematically in given Figure. The radiation emerging
from the source is passed through an interferometer to the sample before reaching a
detector. Upon amplification of the signal, in which high-frequency contributions
have been eliminated by a filter, the data are converted to digital form by an
analog-to-digital converter and transferred to the computer for Fourier-
transformation. The major components of the spectrometer are discussed as
452
22.6.1 Michelson Interferometers
The most common interferometer used in FTIR spectrometry is a
Michelson interferometer, which consists of two perpendicularly plane mirrors,
one of which can travel in a direction perpendicular to the plane ,a semi-reflecting
film, the beam splitter, bisects the planes of these two mirrors. The beam splitter
material has to be chosen according to the region to be examined. Materials such as
germanium or iron oxide are coated onto an infrared-transparent substrate such as
potassium bromide or caesium iodide to produce beam splitters for the mid- or
near-infrared regions. Thin organic films, such as poly (ethylene terephthalate), are
used in the far-infrared region. If a collimated beam of monochromatic radiation of
wavelength λ (cm) is passed into an ideal beam splitter, 50% of the incident
radiation will be reflected to one of the mirrors while 50% will be transmitted to
the other mirror. The two beams are reflected from these mirrors, returning to the
beam splitter where they recombine and interfere. The moving mirror produces an
optical path difference between the two arms of the interferometer. For path
differences of (n + 1/2)λ, the two beams interfere destructively in the case of the
transmitted beam and constructively in the case of the reflected beam.
Figure 22.5 FTIR spectrometer
453
22.6.2 Sources and Detectors
FTIR spectrometers use a Globar or Nernst source for the mid-infrared
region. If the far-infrared region is to be examined, then a high-pressure mercury
lamp can be used. For the near-infrared, tungsten–halogen lamps are used as
sources. There are two commonly used detectors employed for the mid-infrared
region. The normal detector for routine use is a pyro-electric device incorporating
deuterium tryglycine sulfate (DTGS) in a temperature-resistant alkali halide
window. For more sensitive work, mercury cadmium telluride (MCT) can be used,
but this has to be cooled to liquid nitrogen temperatures. In the far-infrared region,
germanium or indium–antimony detectors are employed, operating at liquid helium
temperatures. For the near-infrared region, the detectors used are generally lead
sulfide photoconductors.
22.6.3 Fourier-Transformation
The essential equations for a Fourier-transformation relating the intensity
falling on the detector I(δ) to the spectral power density at a particular
wavenumber v is given by B( v ) as
I ( ) B(v ) cos(2 v )dv
0
where B(v ) I ( ) cos(2 v )d
These two equations are inter-convertible and are known as a Fourier-transform
pair. The first shows the variation in power density as a function of the difference
in path length, which is an interference pattern. The second shows the variation in
intensity as a function of wavenumber. Each can be converted into the other by the
mathematical method of Fourier-transformation. The essential experiment to obtain
an FTIR spectrum is to produce an interferogram with and without a sample in the
beam and transforming the interferograms into spectra of (a) the source with
sample absorptions and (b) the source without sample absorptions. The ratio of the
former and the latter corresponds to a double-beam dispersive spectrum. The major
advance toward routine use in the mid-infrared region came with a new
mathematical method devised for fast Fourier-transformation (FFT). This was
combined with advances in computers which enabled these calculations to be
carried out rapidly.
454
22.6.4 Moving Mirrors
The moving mirror is a crucial component of the interferometer. It has to be
accurately aligned and must be capable of scanning two distances so that the path
difference corresponds to a known value. A number of factors associated with the
moving mirror need to be considered when evaluating an infrared spectrum. The
interferogram is an analogue signal at the detector that has to be digitized in order
that the Fourier-transformation into a conventional spectrum can be carried out.
There are two particular sources of error in transforming the digitized information
on the interferogram into a spectrum. First, the transformation carried out in
practice involves an integration stage over a finite displacement rather than over an
infinite displacement. The mathematical process of Fourier transformation assumes
infinite boundaries. The process of apodization is the removal of the side lobes (or
pods) by multiplying the interferogram by a suitable function before the Fourier-
transformation is carried out. A suitable function must cause the intensity of the
interferogram to fall smoothly to zero at its ends. Most FTIR spectrometers offer a
choice of apodization options and a good general purpose apodization function is
the cosine function, as follows:
F(D) = [1 + cos (πD)]/2
where D is the optical path difference. This cosine function provides a good
compromise between reduction in oscillations and deterioration in spectral
resolution. When accurate band shapes are required, more sophisticated
mathematical functions may be needed. Another source of error arises if the
sample intervals are not exactly the same on each side of the maxima
corresponding to zero path differences. Phase correction is required and this
correction procedure ensures that the sample intervals are the same on each side of
the first interval and should correspond to a path difference of zero. The resolution
for an FTIR instrument is limited by the maximum path difference between the two
beams. The limiting resolution in wavenumbers (cm−1) is the reciprocal of the path
length difference (cm). For example, a path length difference of 10 cm is required
to achieve a limiting resolution of 0.1 cm−1. This simple calculation appears to
show that it is easy to achieve high resolution. Unfortunately, this is not the case
,since the precision of the optics and mirror movement mechanism become more
difficult to achieve at longer displacements of path lengths.
455
22.6.5 Signal-Averaging
The main advantage of rapid-scanning instruments is the ability to increase
the signal-to-noise ratio (SNR) by signal-averaging, leading to an increase of
signal-to-noise proportional to the square root of the time, as follows:
SNR α n1/2
There are diminishing returns for signal-averaging in that it takes an increasingly
longer time to achieve greater and greater improvement. The accumulation of a
large number of repeat scans makes greater demands on the instrument if it is to
exactly reproduce the conditions. It is normal to incorporate a laser monochromatic
source in the beam of the continuous source. The laser beam produces standard
fringes which can ‘line-up’ successive scans accurately and can determine and
control the displacement of the moving mirror at all times.
22.6.6 Computers
The computer forms a crucial component of modern infrared instruments
and performs a number of functions. The computer controls the instrument, for
example, it sets scan speeds and scanning limits, and starts and stops scanning. It
reads spectra into the computer memory from the instrument as the spectrum is
scanned; this means that the spectrum is digitized. Spectra may be manipulated
using the computer, for example, by adding and subtracting spectra or expanding
areas of the spectrum of interest. The computer is also used to scan the spectra
continuously and average or add the result in the computer memory. Complex
analyses may be automatically carried out by following a set of pre-programmed
commands. The computer is also used to plot the spectra.
22.6.7 Spectra
Early infrared instruments recorded percentage transmittance over a linear
wavelength range. It is now unusual to use wavelength for routine samples and the
wavenumber scale is commonly used. The output from the instrument is referred to
as a spectrum. Most commercial instruments present a spectrum with the
wavenumber decreasing from left to right. The infrared spectrum can be divided
into three main regions: the far infrared (<400 cm−1), the mid-infrared
(4000–400 cm−1) and the near-infrared (13000–4000 cm−1).
456
Figure 22.6. Typical FTIR spectra of Aniline
Many infrared applications employ the mid-infrared region, but the near- and far-
infrared regions also provide important information about certain materials.
Generally, there are less infrared bands in the 4000–1800 cm−1 region with many
bands between 1800 and 400 cm−1. Sometimes, the scale is changed so that the
region between 4000 and 1800 cm−1 is contracted and the region between 1800 and
400 cm−1 is expanded to emphasize features of interest. The ordinate scale may be
presented in % transmittance with 100% at the top of the spectrum. It is
commonplace to have a choice of absorbance or transmittance as a measure of
band intensity.
22.7 Self
22.7 SelfLearning
LearningExercise
Exercise
Q.1 Write the formula for population of a rotational level at any temperature.
Q.2 Write the Lagrangian of a system of a diatomic molecule.
Q.3 Write the Frequencies of vibration of C-H in alkenes, alkynes and aromatic
ring.
Q.4 Write the use of moving mirror in FTIR spectrometer.
457
22.8
22.8 Summary
Summary
This unit deals with populations of vibrational and rotational levels at any
temperature. The degeneracy of rotational level as well maximum population for a
particular value of rotational quantum number has been discussed. The degree of
freedoms of a molecules having N atoms as well vibrational degree of freedom
have been discussed. The normal co-ordinates as well as normal mode of
vibrations of a diatomic molecule have been explained. The skeletal vibrational
frequency range and functional frequencies range is also discussed. Finally the
instrumentation required to record the IR spectrum particularly FTIR has been
discussed in detail. All the components of FTIR spectrophotometer have been
discussed in detail.
22.9
22.9 Glossary
Glossary
Degenerate : Number of states having same energy
Degree of freedom : Number of independent co-ordinates required to specify the
state
Lagrangian :Total energy function mechanics
Linear : Along a line
Non-linear : Not along a line (bend)
Transparent : Able to pass
Splitter : Dividing into two or many
Interferometer : Instrument to record the interference
Interferogram : Interference pattern
22.10
22.10Exercise
Exercise
Q.1 Write the formula for population of a vibrational level at any temperature.
Q.2 Discuss the thermal distribution of vibrational and rotational levels.
Q.3 Write the various degree of freedom of a molecule having N atoms.
Q.4 Write the number of vibrational modes of a linear and non-linear molecule
having N atoms.
458
Q.5 Write the Lagrangian equation of motion of a system of a diatomic
molecule.
Q.6 Explain the normal modes and normal co-ordinates.
Q.7 Write the various modes of vibration of a linear and non-linear molecule
with example.
Q.8 Write a short note on skeletal vibration.
Q.9 Write a short note on group frequencies.
Q.10 Write the general regions of skeletal and group frequencies.
Q.11 Write the Frequencies of vibration of C=C bond in alkenes, alkynes and
aromatic ring.
Q.12 Write the basic components of FTIR spectrometer.
Q.13 Write the sources of IR and detectors of IR used in FTIR spectrometers.
Q.14 Discuss the construction and working of FTIR spectrometer.
References
Referencesand
andSuggested
SuggestedReadings
Readings
1. Colin N. Banwell and Elaine M. McCash: Molecular Spectroscopy, Tata
Mcgraw-Hill Education Private Limited, New Delhi, 1994.
2. J. M. Holias: Modern Spectroscopy , John Wiley & Sons, England, 1987.
3. S.L. Gupta, V. Kumar and R.C. Sharma: Elements of Spectroscopy, Pragati
Prakashan, Meerut, 1990.
4. Raj Kumar: Atomic & Molecular Spectra: LASER, Kedar Nath Ram Nath,
Meerut, 2007.
5. G.M. Barrow, Introduction to Molecular Spectroscopy, McGraw Hill, London,
1961.
6. B. Stuart, Infrared Spectroscopy: Fundamentals and Applications, John Wiley
& Sons, Ltd, 2004.
459
UNIT-23
Raman
RamanSpectra,
Spectra,Franck-Condon
Franck-CondonPrinciple
Principle
Structure of the Unit
23.0 Objectives
23.1 Introduction
23.2 Raman Effect
23.3 Classical Theory of Raman Effect
23.3.1 Quantum Theory of Raman Effect
23.3.2 Probability of Transition in Raman Effect
23.33 Vibrational Raman Spectra
23.3.4 Rotational Raman Spectra
23.3.5 Vibrational-Rotational Raman Spectra
23.4 Raman Spectrometer
23.5 Franck Condon Principle
23.6 Illustrative Examples
23.7 Self Learning Exercise
23.8 Summary
23.9 Glossary
23.10 Exercise
References and Suggested Readings
23.0
23.0Objectives
Objectives
This unit is designed to provide basic knowledge about the one of most
important phenomenon called as Raman Scattering or Raman Effect. The classical
as well as quantum theories of Raman Effect will be discussed. It will be explained
here that how the Raman scattering is related to vibration and rotational energy
levels of the molecules and how it can provide the information about the molecular
460
structure. The required instrumentation to observe Raman Scattering will also be
discussed.
23.1
23.1Introduction
Introduction
The scattering of electromagnetic radiation from the solid and there is a
shift in frequency of electromagnetic radiation is called as Raman Effect. The
scattering of these radiations by the solid is related to the vibrational and rotational
energy levels of the molecules of the solids. Here the basic theories of Raman
effect, origin of different spectral lines and various branches of these lines are
explained. Finally the Raman Spectrometer is discussed in detail.
23.2
23.2Raman
RamanEffect
Effect
When a monochromatic radiations or radiations of very narrow frequency
band are scattered by a solid then the scattered radiations not only consists of
radiations of incident frequency but also radiations of frequencies above and below
that of incident beam frequency. This type of scattering in which the frequency of
incident beam undergoes a definite change was observed and was studied by
Raman in 1928 and is called as Raman Effect. If vi is the wavenumber of incident
wave and vs is the wavenumber of scattered wave then the Raman shift is given by
(v ) rmn vi vs
This difference is the characteristic of the material and it does not depend upon the
wavenumber of the incident radiation. If (v )rmn is positive ,then Raman spectra is
said to have Stokes lines and if (v )rmn is negative ,then the Raman spectra is said
to have anti-Stokes lines.
The intensity of Stokes lines is higher as compared to anti-Stokes lines. The
Raman shift (v )rmn lies within the range 100-3000 cm-1, which fall in the far and
near infra-red region of the spectrum. This shift suggests that the changes in the
461
energy of scattered radiations in the Raman Effect correspond to the energy
changes accompanying rotational and vibrational transitions in the molecules of
the materials.
23.3
23.3Classical
ClassicalTheory
TheoryofofRaman
RamanEffect
Effect
If an atom or a molecule is placed in an electric field ,then the electrons and
the nuclei are displaced relative to each other i.e. an electric dipole moment is
induced in the molecule due to this relative displacement of electrons and nuclei. It
is also called as molecular polarization by the external electric field. Let E is the
intensity of electric field and µ is the magnitude of induced dipole moment then
E
where α is the polarizability of the molecule. The intensity of the electric field of
the electromagnetic wave of frequency can be expressed as
E E0 Sin(2t )
So the polarizability of the molecule is given by
E0 Sin(2t )
462
So the interaction of radiation of frequency induces a dipole moment in the atom
or molecule. This dipole moment oscillates with same frequency . So from the
classical theory, this oscillating dipole will scatter or emit radiation of frequency
i.e. frequency of incident radiations. It is called as Rayleigh scattering.
In the above discussion no internal motion i.e. rotation and vibration of the
molecule is considered. Let us first consider the effect of vibrational motion of a
diatomic molecule. When the two nuclei of the molecule vibrate along the line
joining them then the polarizability of the molecule will change. The change in the
polarizability α, with small displacement x from equilibrium position is given by
x
0
A
where 0 is the equilibrium polarizability is the rate of variation of
polarizability with displacement and A is the vibrational amplitude. If the molecule
executes the simple harmonic motion ,then the displacement from the mean
position is given by
x ASin(2vt )
where v is the frequency of vibration of the molecule. So the polarizability of the
molecule is given by
0 Sin(2v t )
So the induced dipole moment is given by
0 E0 Sin(2t ) E0 Sin(2t ) Sin(2vt )
1
0 E0 Sin(2t ) E0 [Cos 2 ( v )t Cos 2 ( v )t ]
2
Thus the induced dipole moment oscillates with frequencies of radiations , v
and v . The first frequency is same as that of incident radiation i.e. Rayleigh
scattering and last two frequencies are due to Raman scattering. The vibrational
shift is equal to v .
Now let us consider the effect of rotation of molecule on polarizability.
During the rotation of the molecule the orientation of the molecule with respect to
electric field of radiation changes, therefore the molecule is not isotropic, it shows
463
different polarizability in different directions. The polarizability of the molecule
varies with time. The variation of polarizability can be expressed as
0 Sin2 (2r )t
where r is the frequency of rotation. The polarizability changes at a rate twice the
frequency of rotation, therefore in place of r we have written 2 r . The induced
dipole moment is given by
0 E0 Sin(2t ) E0 Sin(2t ) Sin(4r t )
1
0 E0 Sin(2t ) E0 [Cos 2 ( 2 r )t Cos 2 ( 2 r )t ]
2
The Raman lines will have frequencies , 2r and 2r . The Raman shift
will be 2 r i.e. equal to twice the frequency of rotation.
So we conclude that in the scattered radiation, there will be vibrational lines at v
on either sides of Rayleigh line and also rotational Raman lines at 2r on either
sides of . It is not necessary to have a permanent electric dipole moment to show
Raman spectra. So the homo-nuclear molecules also show Raman spectra even
though they are IR inactive.
23.3.1 Quantum Theory of Raman Effect
When electromagnetic waves are incident on the molecules of a substance
then due to absorption of these radiations the molecules are raised to higher state.
Now if the molecules return to their original state, then the frequency of radiation
emitted is same as that of incident light, but if they return to a higher or lower state.
Let us consider a molecule in its initial state having energy E and it is exposed to
incident radiations of wavenumber vi . Due to absorption of this radiation the
molecule is raised to higher energy state having energy E hcvi . Now suppose that
the molecule returns to a level of energy level of energy E lying above E , by
losing energy hcvs and wavenumber of scattered radiations is vs .
E hcvi hcvs E
E E hc(vi vs ) hc(v ) rmn E
The Raman shift is equal to the difference in energy of two levels represented by
E and E . The sign of (v )rmn depends upon ( E E ), if E > E then (v )rmn is
positive and hence Raman Stokes lines are produced. If E < E then (v )rmn is
464
negative and hence Raman anti-Stokes lines are produced. Classically the intensity
of Stokes and anti-Stokes lines should be same but experimentally it is found that
the intensity of Stokes lines is higher as compared to anti-Stokes lines.
23.3.2 Probability of Transition in Raman Effect
When an atom or molecule is placed in electric field of intensity E the
electrons and nuclei are displaced in such a manner so as to induce electric dipole
moment µ given by
E
where α is the molecular polarizability. Now if the two nuclei vibrate along the
line joining them ,then the polarizability will vary. For small displacement the
variation in the polarizability is expressed as
x
0 ,
A
where 0 the equilibrium polarizability is is the rate of variation of polarizability
with displacement and A is amplitude of vibrations. Let us consider the x
components of polarizability and determine the transition probability as
Pmn ( x) m ( xx Ex ) n d (A)
where αxx is the polarizability in the x direction when the electric field Ex is acting
in the same directions. The variation of polarizability αxx during the oscillation of
molecule is given by
x
xx xx0 xx (B)
A
Therefore from equation (A) and (B) we have
Ex
Pmn ( x ) xx0 E x m n d xx m n d (C)
A
So we conclude from equation (C) as
1. The first term of this equation is zero except m = n. This term gives rise to a
transition which does not involve the vibrational or rotational transitions. This
term gives the transition probability of Rayleigh scattering.
2. For Raman scattering m ≠ n, the first term is zero, while for non zero of
second term xx must change during the vibrations.
465
3. For the molecule to be Raman active it is necessary that the molecular
polarizability must change in any direction during the rotations of the
molecule.
23.3.3 Vibrational Raman Spectra
The vibrational Raman spectrum arises due to transition of molecule from
one vibrational level to other vibrational level of same electronic state. Quantum
mechanically if xx is not zero, the molecule will show Raman scattering. From the
study of matrix element Pmn ( x) of the polarizability, it is found that in case of
harmonic oscillator the same selection rule holds for Raman scattering as in case of
infra-red spectrum i.e.
v 1
The transition takes place only adjacent vibrational levels i.e. from one level to
next upper level (Stokes lines) or to the next lower level (anti-Stokes lines). Thus
in the Raman spectrum there will be one Stoke and one anti-Stoke line which are
shifted by an amount v vib to both sides of the original line.
v vib
G (v 1) G (v) v
At ordinary temperature most of the molecules are in their lowest vibrational state
i.e. v = 0, so majority of transitions will be of the type v = 0 to v = 1. A small
number of molecules occupy the v = 1 level which may undergo the transitions as
v = 1 to v =2 (Stokes line) or from v = 1 to v = 0 level (anti-Stokes line). The
intensity of these will be weak because of small number of molecules in this state.
Thus the intensity of the Stokes-Raman lines corresponding to transition v = 0 to
v = 1 is much greater than that of anti-Stokes Raman lines corresponding to
transition v = 1 to v = 0. At high temperature the number of molecules in higher
vibrational levels increases so the intensities of anti-Stokes lines increases.
The vibrational energy of a diatomic molecule is given by
1 1
Ev (v ) hcv (v ) 2 hcxv
2 2
For transition v =0 to v = 1 giving very strong vibrational Raman line
E E (1 2 x)hcv
The Raman shift is given by
466
(v )vib (1 2 x)v v0
where v0 is equal to the frequency of the centre of the fundamental vibrational
band in the infra-red spectrum of the molecule.
23.3.4 Rotational Raman Spectra
These spectra arise due to transition of the molecule from one rotational
energy state to the other rotational state of the same vibrational state. These lines
appear on both sides of Rayleigh line. The selection rule for rotational Raman
transition is different from that of purely rotational transitions (for infra-red). For
the Raman Effect the selection rules for transition between rotational levels are as
J 0, 2
The transition corresponding to J 0 represents no change in the molecular
energy i.e. there is same frequency of scattered Raman radiation (Rayleigh
scattering). The transition corresponding to J 2 gives Stokes lines while
J 2 gives the anti-Stokes lines.
The rotational energy levels of a linear molecule are represented by
h2
Er J ( J 1)
8 2 I
For transition J 2 , the value of rotational shift of Stokes lines is given by
h
( v ) rot {( J 2)( J 3) J ( J 1)}
8 2 cI
h
(v )rot 2 B(2 J 3) , Where B
8 2 cI
For transition J 2 , the value of rotational shift of anti-Stokes lines is given by
(v )rot 2B(2 J 3)
In more general for the Raman Shift due to rotational motion of the molecule is as
(v )rot 2B(2 J 3) ,
where J = 0, 1, 2, 3, .... etc.
The wavenumbers of the corresponding spectral lines are given by
v vexc (v )rot , where vexc is the wavenumber of exciting
radiations.
467
23.3.5 Vibrational-Rotational Raman Spectra
Theoretically it is possible for vibrational and rotational transitions to take
place simultaneously in a Raman transition, the selection rule is as v 1 and
J 0, 2 .
For a diatomic molecule vibrational-rotational energy levels are given by
1 1
Evr hc{v (v ) vx (v ) 2 } BhcJ ( J 1)
2 2
where v = 0, 1, 2, 3 ...etc. and J = 0, 1, 2, 3..... , etc.
In terms of wavenumber
1 1
vvr v (v ) vx(v ) 2 BJ ( J 1)
2 2
Applying selection rules
J 0 v (Q) v0 cm-1, For all J
J 2 v ( S ) v0 B(4 J 6) cm-1, J = 0, 1, 2, 3, ....
J 2 v (O) v0 B(4 J 6) cm-1, J = 2, 3,4, .....
where v0 v (1 2 x) , and O, Q, S refers to O branch, Q branch, R branch
respectively.
468
The Stokes lines will occur at
v (Q) vexc v (Q) vexc v0 cm-1, for all value of J
v (O) vexc v (O) vexc v0 B(4 J 6) cm-1 , for J = 2,3,4, ..
v ( S ) vexc v ( S ) vexc v0 B(4 J 6) cm-1, for J = 0, 1, 2, ...
The anti-Stokes lines will occur at
v (Q) vexc v (Q) vexc v0 cm-1, for all value of J
v (O) vexc v (O) vexc v0 B(4 J 6) cm-1 , for J = 2,3,4, ..
v ( S ) vexc v (S ) vexc v0 B(4 J 6) cm-1, for J = 0, 1, 2, ...
23.4
23.4Raman
RamanSpectrometer
Spectrometer
The instrument required to record the Raman scattering is called as
Raman Spectrometer. The recording of the Raman spectrum essentially requires
illumination of sample with monochromatic radiations and detection of scattered
radiations at right angle to incident radiations. The basic components of the Raman
Spectrometer are as :
469
1. Exciting source: In the Raman spectrometer we need a monochromatic
source of radiations. For this purpose one particular line of mercury arc spectrum is
selected. The choice of the wavelength of this line depends upon the intensity of
the line. Nowadays in Raman spectrometer a Helium-Neon laser beam is used.
2. Sample Tube and Sample: The material of the sample tube is either glass
or quartz. The tube is shaped along with associated reflectors in a way so as to
direct much of the incident light into the sample. The length of the tube is
20-30 cm and 12 cm in diameter. To avoid multiple reflections the back of the tube
is horn-shaped and blackened. The other end of the tube is made optically flat so
that scattered radiations do not suffer any distortion on their exit. The Raman tube
is protected from heat generated by lamps by means of a glass jacket through
which water circulates. The Raman spectrum can be recorded with solid, liquid and
gas phase samples but the liquid sample is more preferred because it easy to handle
it. The quantity of the liquid sample required is between 10-100 mL. Water is a
good solvent because of its weak Raman spectrum.
3. Filters: Liquid filters are placed between the source and the sample tube in
order to remove high energy radiations that may cause photodecompositions, to
470
isolate single exciting line and to remove the continuous spectrum in the region
occupied by the Raman line.
4. Optical system: The optical system is designed so that the maximum
amount of scattered Raman radiation is accepted by the spectrometer. A suitable
spectrograph, with prism or grating having wide aperture and medium dispersion is
preferred.
23.5
23.5Franck
FranckCondon
CondonPrinciple
Principle
The Franck Condon principle is related to electronic spectra of the
molecules. The electronic spectra of the molecule arise when the electrons in the
molecules are excited to higher energy state. The energy involved in this is large so
the electronic spectra of the molecules fall in the visible and ultraviolet region of
electromagnetic spectrum. The electronic spectra arise due to change in the
arrangement of molecular electrons. A small change in electronic energy is
accompanied by a large change in the vibrational energy of the molecule and a
small change in vibrational energy is accompanied by a large change in rotational
energy of the molecule. The vibrational energy changes cause the appearance of
various bands and the rotational energy changes cause formation of various lines in
each band.
471
The probability of transition between two given vibrational levels of two
different electronic states is given by the Franck-Condon principle. According to
this principle “The transition between two vibrational levels should start from
extreme position of the levels and they are represented by vertical lines”.
The rearrangement of the electrons in a molecule is 1000 times faster than the time
period of vibrations of nuclei. During the electronic transition the inter-nuclear
distance does not change appreciably so the transitions are represented by vertical
lines. Further, the transitions are most probable when the nuclei in their mean
positions. The nuclei spend maximum time in these states because of zero kinetic
energy in these states. The square of the vibrational eigen function is maximum at
extreme positions implying the probability of finding the nuclei is maximum there.
However for lowest vibrational state v = 0, quantum mechanics predicts that the
most probable position for nuclei is the equilibrium position re. Thus the most
probable inter-nuclear distance for the vibrational levels other than v = 0,
corresponds to extreme positions and mid-position for v =0. So, the transitions will
start from extreme position for levels other than v = 0 and for v = 0 the transition
will start from mid-point.
23.6
23.6Illustrative
IllustrativeExamples
Examples
Example 1 The wavelength of the exciting line in Raman scattering is 5460 A0
and stokes line is observed at 5520 A0 . Find the wavelength of anti-Stokes line.
Sol. The Raman shift is given by
(v ) rmn vi vs
1
vi 8
18315cm 1
5460 10
1
vs 8
18116cm 1
5520 10
( v ) rmn 18315 18116 199cm 1
The wavenumber of the anti-Stokes line is given by
(vs ) anti stokes vi ( v ) rmn 18315 199 18514cm 1
The wavelength of anti-Stokes line is given by
1
5401A
18514
472
Example 2 The exciting radiations has wavelength 4358 A in Raman spectrum of
a substance which show lines at (v )rmn =608, 846, 995, 1599 and 3064 cm1 . At
what wavelength these lines will appear if the exciting source has wavelength
5461 cm1
Sol. The wavenumber of the exciting line
1
vi 8
18312cm 1
5461 10
Since the difference remains the same ,then the wavenumber of Raman lines are as
vs vi (v )rmn
So the wavenumbers are as
vs1 18312 608 17704cm 1
vs 2 18312 846 17466cm 1
vs 3 18312 995 17317 cm 1
vs 4 18312 1178 17134cm 1
vs 5 18312 1599 16113cm 1
vs 6 18312 3064 15248cm 1
Example 3 A substance shows a Raman line at 4567 A0 when exciting line
4358 A0 was used. Find the positions of Stokes and anti-Stokes lines for the same
substance when exciting line 4047 A0 is used.
Sol. The Raman shift is given by
(v ) rmn vi vs
1
vi 8
22946cm 1
4358 10
1
vs 21896cm 1
4567 108
( v ) rmn 22946 21896 1050cm 1
The wavenumber of the other exciting line is
1
vi 24710cm 1
4047 108
So the wavenumber of Stokes line is as
473
vstoke 24710 1050 23660cm 1
and the wavenumber of anti-Stokes line is
vanti stoke 24710 1050 25760cm 1
The wavelengths of Stokes and anti-Stokes lines are
1
stoke 4226.5 A
23660
1
anti stoke 3882 A
25760
Example 4 In the rotational Raman spectrum of a molecule the displacement from
exciting line is represented by (v )rot. (62.4 41.6 J ) cm-1 . Calculate the
moment of inertia of the molecule.
Sol. The rotational Raman shift is given by
(v ) rot . 2B(2 J 3)
(62.4 41.6 J ) 2B(2 J 3)
3 3
41.6( J ) 4 B ( J )
2 2
41.6
B 10.4cm 1
4
The rotational constant B is related to moment of inertia I as
h h
B so I
8 2 Ic 8 2 Bc
6.62 1027
I
8 (3.14)2 10.4 3 1010
2.7 1040 gm.cm 2
23.7 Self
23.7 SelfLearning
LearningExercise
Exercise
Q.1 What is Raman Effect ?
Q.2 Explain the origin of Stokes and anti-Stokes lines.
Q.3 Discuss the quantum theory of Raman Effect.
Q.4 Write the selection rules for Raman vibrational-rotational transitions.
474
23.8
23.8 Summary
Summary
The aim of this unit is to study the spectroscopy technique known as Raman
Effect. This technique can be used in place of IR spectroscopy technique but this
technique is more versatile as compared to IR technique. The IR technique fails to
provide information when the molecules are homo-nuclear in the materials. Since
the principle of Raman Effect involves the polarization of molecules by the
radiations ,so the information can also be obtained from this technique. Here first
the definition of Raman Effect has been discussed and then its classical and
quantum theories have been developed. The quantum theory is useful to provide
the information about the intensity of Stokes and anti-Stokes lines. The selection
rules for transitions among the various vibrational levels as well between rotational
levels have been discussed. The basic components of Raman spectrometer have
been discussed. Finally there is the discussion on the Franck-Condon principle
which predicts the transition probability between two electronic states.
23.9 Glossary
23.9 Glossary
Homo-nuclear : Same type of nucleus
Hetero-nuclear: Different type of nucleus
Polar : Having positive and negative charge
Oscillating : Periodically varying
Polarizability : measurement of tendency to be polarized
Band : Group of energy levels or spectral lines
Shift : Kind of displacement
Accompanying : Simultaneously
Photodecomposition : Dissociation by radiations
Scattering : Absorption and re-emission of radiations
Inter-nuclear : Between two nucleus.
23.10Exercise
23.10 Exercise
Q.1 What is Rayleigh line ?
Q.2 Explain Stokes and anti-Stokes lines ?
475
Q.3 Explain the variation of polarizability of molecule with the electric field of
electromagnetic radiations.
Q.4 Explain why the intensity of Stokes and anti-stokes lines is not same?
Q.5 Write the basic components of Raman spectrometer.
Q.6 Explain the Franck-Condon principle.
Q.7 Discuss the classical theory of Raman Effect.
Q.8 Explain the fine structure of Raman spectral lines.
References
Referencesand
andSuggested
SuggestedReadings
Readings
1. Colin N. Banwell and Elaine M. McCash: Molecular Spectroscopy, Tata
McGraw-Hill Education Private Limited, New Delhi, 1994.
2. J. M. Holias: Modern Spectroscopy , John Wiley & Sons, England, 1987.
3. S.L. Gupta, V. Kumar and R.C. Sharma: Elements of Spectroscopy, Pragati
Prakashan, Meerut, 1990.
4. Raj Kumar, Atomic & Molecular Spectra: LASER, Kedar Nath Ram Nath,
Meerut, 2007.
5. G.M. Barrow, Introduction to Molecular Spectroscopy, McGraw Hill, London,
1961.
476
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