Electronic polarization

• For calculating the effect of

electronic polarization,
• We consider an idealized atom
with perfect spherical
symmetry.  It has a point like
charge + ze in the nucleus, and
The exact opposite charge – ze
homogeneously distributed in
the volume of the atom, which
is       
4 3
V  R
3
with R = radius of the atom
Ques: Density of electrons?
Ques: Lorentz force = coulomb force =?
The density of electrons (Charge/Volume of atom) is then
3 ze
 
4 R 3

In the presence of an electric field E ;

Lorentz force: F1=-zeE acts on charges.

The positive charge in the nucleus and the center of the

negative charges from the electron "cloud" will thus
experience forces in different direction and will become
separated. We have the idealized situation shown in the
image in last slide.
 • The attractive force (between opposite charges)
F2 is given by
(charge of nucleus)(negative charge encolesd in sphere of radius d)
F2 
4 0 d 2
 - ( ze) 2 
 3 
d
 4 0 R 
 negative charge encolesd in sphere of radius d
4 3  d 3 - zed 3
= -ze  3
4 3 R 3
R

* Q= charge density x volume

 • Equating F1 and F2 we have equilibrium distance dE as
4 0 R 3 E
dE 
ze
• Therefore the induced dipole moment is

  zed E  4 0 R 3 E

• As polarization is dipole moment per unit volume so

P  4 0 NR 3 E and
P
=  4 NR 3
0E

And Electronic Polarizability:

   .E Where αe is defined by
•Ques: What is the Dimension Electronic polarizability.
of Polarizability?  e  4 0 R 3
P = NeE = o(r -1)E
This gives
o(r -1) = Ne
Here N is the number of dipoles per unit volume.

There are a number of interesting points about the

last result:
1. We have justified the "law" of a linear relationship
between E and P for the electronic polarization
mechanism (sometimes also called induced
polarization).
2. We can easily extend the result to a mixture of different
atoms: All we have to do is to sum over the relative
densities of each kind of atom.
 We can easily get an order of magnitude for .
Taking a typical density of N≈ 3 x 1025 m– 3 and
R ≈ 6 x 10– 12 m, we obtain ≈ 8.14 x 10–5,     
and εr =1. 000 0814 P  4 0 NR E and
3

P
=  4 NR3
Note: 0E
1. The values of molecular dipole moments are usually
expressed in Debye units(3.3 x10-30 Cm). The Debye unit,
abbreviated as D, equals 10-18 electrostatic units (e.s.u.).
2. The permanent dipole moments of non-symmetrical
molecules generally lie between 0.5 and 5D.
3. In the case of polymers and biopolymers one can meet
much higher values of dipole moments ~ hundreds or
even thousands of Debye units.
 2. Ionic polarization
• Consider a simple ionic
crystal, e.g. NaCl.
• Each Na+ - Cl– pair is a natural
dipole, no matter how you pair
up two atoms.

• The polarization of a given

volume, however, is exactly
zero because for every dipole
moment there is a neighboring
one with exactly the same
magnitude, but opposite sign.
– Note that the dipoles can not
rotate; their direction is fixed.
• In an electric field, the
ions feel forces in
opposite directions.
• For a field acting as
shown, the lattice distorts
a little bit (hugely
exaggerated in the
drawing) 
• The Na+ ions moved a bit
to the right, the Cl– ions
to the left.
• The dipole moments
between adjacent NaCl -
pairs in field direction are
now different and there is
a net dipole moment in
a finite volume now.
Ques: How large is d ?
 How large is d ?
• The force F1 increasing the distance is given by 
F1  =  q · E  
with q = net charge of the ion.
• The restoring force F2: for d << d0, we can write 
F2  =  kIP · d 
with kIP being the "spring constant" of the bond.
– kIP can be calculated from the bond structure and by the shape of
interatomic potential, e.g. the modulus of elasticity or Youngs
modulus. If we do that we simply find  kIP  = Y  · d0 with Y = Youngs
Modulus, and d0 = equilibrium distance between atoms (in the
Hence F2=Y.d0.d
absence of E).
• From force equilibrium. i.e. F1 – F2 = 0, Hence 
qE Ques: μ=?, P=?
d 
Yd 0
 Other relations
2
q E
 and
Yd 0
Nq 2 E
P= .
Yd 0
Exercise: Find out χ and  r
 Summary: Ionic polarization
In the presence of E:
qE
Net Displacement: d
Yd 0
q2 E
Dipole moment:  and
Yd 0
Nq 2 E
Polarization: P= .
Yd 0
Find out χ and  r
P Nq 2
  
0E  0Yd 0

And εr = (+1)
 Orientation Polarization
• In the case of Orientation polarization (sometime called Dipolar
polarization) we have a material with built-in dipoles that are
independent of each other, i.e. they can rotate freely - in sharp contrast
to ionic polarization.
• The prime example is liquid water,
– where every water molecule is a little dipole that can have any orientation
with respect to the other molecules.
– Moreover, the orientation changes all the time because the molecules
moves! (Orientation polarization for dielectric dipoles thus is pretty much
limited to liquids)
• It is like a snapshot (2D) with a very, very short exposure time. A few
nanoseconds later the same piece of water may look totally different in
detail, but pretty much the same in general.
– In a three-dimensional piece of water the blue and green circles would not
have to be in the same plane; but that is easy to imagine and is difficult to
draw
Orientation polarization: visualize it
in water
• Water molecules that form natural dipoles.
– because the negatively charged oxygen atom and the two positively
charged H - atoms have different centers of charge.
– Each molecule carries a dipole moment which can be drawn as a vector
of constant length.
– If we only draw a vector denoting the dipole moment, we get - in two
dimensions - a picture like this:

• The sum of all dipole moments will be zero, if the dipoles are
randomly oriented.
• If we now introduce a field E, the dipoles would have a tendency to
turn into the field because that would lower their energy.
• The dipoles are not sitting still, but moving around and rotating all the
time - because they contain thermal energy and thus also some
entropy.

• The electrical field induces average orientation in field direction.

– Most of the time an individual dipole points in all kinds of directions.
– The "real" picture (in the sense of a snapshot with a very short exposure
time) looks like this: 

With out Field With Field

• The orientation of all dipoles is just a little bit shifted so that an average
orientation in field direction results. In the picture, the effect is even
exaggerated!
 Energy of a dipole in Electric field:
• Consider a Polar molecule E
(1)
which caries a permanent +q
dipole moment μ (qd, like
water molecule) is placed in an d
electric field E.
• The Potential energy is given
by; -q (2)
U= -μ.E=- μEcos(θ)

• In thermal equilibrium the relative number of molecules with the potential

energy U is proportional to (Boltzmann statistics)

U  E cos( )
e kT
e kT
 Number of dipoles in a solid angle:
• Let n(θ) be the number of dipoles per unit solid angle at
θ, we have
 E cos( )
n( )  n0 e kT
.

• The number of dipoles in a solid angle d

 E cos 
n0 exp( )2 sin  d
kT
********************************************************************************************
Note:
Where dr.dS/r3
Can be calculated
as follows:
 Average Dipole Moment
• The average dipole moment in an electric field is the net moment
of the assembly divided by the total number of dipoles


  
 0
n0 exp(  E cos  / kT )2 sin  (  cos  ) d

 0
n0 exp(  E cos  / kT )2 sin  d
– Therefore,
  E cos a
1
 cos  e sin  d  xdx
x
kT
e
 2 1
 0
  E cos
 a

 1 a a

e sin  d  dx
x
kT
e
0
2 a

1 [ xe x  e x ] aa e a  e  a 1 1
 x a
 a a
  cot anha   L(a ),
Coth(a)
a [e ] a e e a a
L(a) is called Langeven function
where  E cos  x E  a
kT and kT
    .L ( a ) Where Ps is saturation polarization and
N v   N v . .L(a ) Po is orientation Polarization.

Po  Ps .L(a ) Case I: when a is very high : at Low Temp;

a>>1 L(a)=1, Po = Ps
where
Case II: when a is very Low: at high Temp;
 .E
a a<<1, 1 a a3
Coth(a)     ....
kT a 3 45

Langevin Hence L(a) ≈ a/3 or Po = Ps. a/3

y y=1/3 a
•In Fig. the Langeven function L(a) is
L(a)
1.0
1.0 y=1
y=1 plotted against a.
0.8
0.8

0.6
0.6
y=L( aa))
y=L(
• L(a) has a limiting value 1, which was to
0.4
0.4
be expected since this is the maximum of
cos..
0.2
0.2

0.0
0.0
00 11 22 33 44 55 66 77 88

a aa
 Nv  E 2
Orientation Polarization Po  and
3kT
Po   o N v E
Hence
 2
1
Orientation Polarizability o   o 
Or Dipolar Polarizability 3kT T

Note: Derivation shows that “ tendency of the extended field to

align the dipoles is contracted by thermal motion resulting in a
decreasing value of Po with increasing T
 Total Polarizability of Polyatomic Gas:

• P = Pe + P i + P o
P = NEαe + NEαi + NEαo = ε0 (εr - 1) E
Hence

(εr - 1) =χ =N.α/ ε0

Where α is called Total Polarizabilty

 2
  e  i 
3kT
Is known as Langevin- Debye Equation