MSSBAUER

SPECTROSCOPY AND
ITS APPLICATIONS
HYPERFINE
INTERACTIONS
HYPERFINE INTERACTIONS
Previous treatment dealt with the transitions
between unperturbed nuclear energy levels of
bare nuclei
In reality, nuclei are embedded in electric and
magnetic fields created by the atomic electrons
of the Mossbauer atom and charge
distributions its environment
Nuclei are positively charged and possess
nuclear moments
These moments interact with the electric and
magnetic fields in the nuclear region
The consequent perturbations of the nuclear
levels are called Hyperfine Interactions

HYPERFINE INTERACTIONS
The hyperfine interactions measured by
Mossbauer Spectroscopy are a function of a
nuclear part, and an atomic part.
The atomic part relates to chemical and solid
state information and is a complex function of the
electronic energy levels of the atom.

HYPERFINE INTERACTIONS
There are three main hyperfine interactions:
i. The isomer (or chemical) shift: (electric
monopole interaction)
ii. The quadrupole splitting: (electric
quadrupole interaction)
iii. The magnetic hyperfine splitting (magnetic
dipole interaction)
TYPES OF HYPERFINE
INTERACTIONS
All of these (particularly iii.) show time
dependent effects (relaxation) if they vary on
the Mssbauer timescale.
Electric Dipole interaction does not exist due
to symmetry of the nuclear charge distribution
Higher order interactions are negligible
TYPES OF HYPERFINE
INTERACTIONS
Diagram
H.I.
nucleus
atom
Solid
Electric Hyperfine Interactions
The nuclear charge density is
n
(r), and the
potential is V(r) within the nucleus
The total electrostatic interaction
t = d r V r E
n el
Electric Hyperfine Interactions
Taylor series expansion


Thus



( )

= =
+
|
|
.
|

\
|
c c
c
+
|
|
.
|

\
|
c
c
+ =
3
1
0
2
0
3
1
0
2
1
j , i
j i
j i
i
i
i
... x x
x x
V
x
x
V
V r V
( ) ( )
( )
}

} }

+ t
|
|
.
|

\
|
c c
c
+
t
|
|
.
|

\
|
c
c
+ t =
=
=
... d x x r .
x x
V
d x r .
x
V
d r V E
j i n
j , i
j i
i n
i
i
n el
3
1
0
2
0
3
1
0
2
1
The first term is eZV
0
.
It represents the interaction of the nucleus as a
point charge and the potential at the nuclear
site
This term contributes a constant value to the
potential energy of the crystal; it is of no
interest
Electric Hyperfine Interactions
The second term represents the electric dipole
interaction, and vanishes due to symmetry of
the nuclear charge distribution
Electric Hyperfine Interactions
The third term
(c
2
V/cx
i
cx
j
)
0
= V
ij
is a (3x3) second-rank
tensor. We diagonalize this tensor (principal
axes) such that the only non vanishing terms
are V
ii
.
Electric Hyperfine Interactions
Electric Hyperfine Interactions
Thus, the third term is rewritten as






( )
( ) ( )

}

}

}
= =
=
t + t
|
|
.
|

\
|
=
t =
3
1
3
1
2
2
2
3
1
2
6
1
3 2
1
2
1
i i
n ii i n ii
i
i n ii
d r r V d
r
x r . V
d x r . V E
Nuclear Quadrupole Moment
The diagonal tensor elements of the
quadrupole moment in the principal axes
system are
( ) t = d r x r Q
i n ii
2 2
3
Poisson Equation
In cgs system
V
2
V + 4t
e
= 0
Thus,
2
0
3
1
0
2
0 4 t =
|
|
.
|

\
|
= V
=
e V V
i
ii
Electric Hyperfine Interactions
Thus
( ) ( )
Q I
i
ii ii n
E E
Q V d r r e E
+
+ t t =
=
3
1
2
2
6
1
0
3
2
Electric Monopole Interaction
Notice that



Thus
t Ze . r d r r
n
2 2
2
2
2
0
3
2
r Ze E
I
t =
ISOMER (CHEMICAL) SHIFT arises
because the nucleus has different radii in the
ground and excited states, and the s-electron
densities at the nucleus are different in
source and absorber.

Electric Monopole Interaction
Isomer Shift
The absorption line is shifted by:



Change in Absorber Source
nuclear radii


( ) ( )
2 2
2 2
0 0
5
4
S
s
A
s
R
R
R Ze
A
t = o
Isomer Shift
The corresponding Doppler velocity
( ) ( )
2 2
2 2
0 0
5
4
S
s
A
s D
R
R
R Ze
E
c
v
A
t =

Origin of isomer shift
Isomer Shift
source absorber
E
S

E
A

E
0
E
0

Resulting effect
Isomer Shift
R
e
l
a
t
i
v
e

t
r
a
n
s
m
i
s
s
i
o
n

0
v(mm/s)
o
Relativistic effects are appreciable for large Z,
and cause modification of the wave function
near the nucleus
Using Dirac wave function and first-order
perturbation theory, the relativistic correction
is simply multiplying the result by the factor
S(Z).

Relativistic Effect on Isomer Shift
Fe
26
S(Z) = 1.32
Sn
50
S(Z) = 2.48
Np
93
S(Z) = 19.4
This problem is not significant in Mossbauer
effect, since the factor is constant for all
compounds of a given nuclide
Relativistic Effect on Isomer Shift
Example

Fe
2+
3d
6
~ 1.5 mm/s
Fe
3+
3d
5
~ 0.5 mm/s


Isomer Shift Values
Nuclear levels with I > have a quadrupole
moment (eQ) due to the deviation of the
charge distribution from spherical symmetry.
This interacts with the electric field gradient
(EFG) at the nucleus (V
xx
V
yy
V
zz
in the
Cartisian coordinate system).

Electric Quadrupole Interaction
Electric Quadrupole Moment
Choosing the z-axis as the axis of quantization,
the electric quadrupole moment for nuclear
charge distribution of cylindrical symmetry is
defined as
( )( ) ( ) ( )
} }
t u = t d cos r r d r z r
e
Q
n n
1 3 3
1
2 2 2 2
Electric Quadrupole Moment
Q > 0 for elongated (cigar-
shaped) nucleus

Q < 0 for flattened
(pancake-shaped) nucleus
Q = 0 for spherical charge
distribution

Diagram
z
Changes in the quadrupole interaction energy
observed in different compounds of a given
Mossbauer atom are associated with changes
in EFG.
Changes in EFG lead to information about the
molecular and electronic structure of the
Mossbauer atom
Electric Field Gradient
Electric Field Gradient
In the principal axis system, we choose the axes such
that

yy xx zz
V V V > >
Electric Field Gradient (EFG)
The EFG is specified by two independent
parameters

V
zz
(=eq) and =

Principal Assymetry
component parameter

V
xx
- V
yy
V
zz
q = 0 for 3-fold or 4-fold axis of symmetry
passing through the nucleus (EFG is axially
symmetric)
EFG = 0 in a system with two mutually
perpendicular axes of 3-fold or higher
symmetry

Electric Field Gradient
Lattice contribution: from surrounding ions in
non cubic symmetry
Valence electron contribution: from
anisotropic electron distribution in the valence
shell of the Mossbauer atom
Sources of EFG
Lattice Contribution
For a point charge q
k
at r
k
from the nucleus, the
potential is q
k
/r at the nucleus
The corresponding EFG is
5
2
3
r
r x x
q V
ij j i
k ij
o
=
Summing over all surrounding ions, and using the
principal axes system
( ) ( )

u =
n
k
k k k
lat
zz
cos r q V
1
2 3
1 3
Lattice Contribution
( )
=

| u = q
n
k
k k k k
lat
zz
lat
cos sin r q
V
1
2 3
2 3
1
The antishielding effect, manifested by the
distortion of the electronic shells due to
interactions with the noncubic charge
distribution, amplifies the lattice
contribution by about 10 times in iron
compounds (Sternheimer)
Lattice Contribution
Valence Contribution
Crystal field theory for ionic compounds: sum
over contributions from all electrons in the
valence atomic shell


Or
( ) ( ) u =

=

n
k
k k
val
zz
cos r e V
1
2 3
1 3

( ) ( )
3
1
2
1 3

=
u =
k
n
k
k
val
zz
r cos e V
In covalent compounds, MO calculations
are more suitable.
Those include contributions from ligand
atomic orbitals as well as valence shell
contributions
Valence Contribution
This anisotropic charge distribution in the
valence shell produces deformation in he
inner orbitals, leading to a correction in the
valence contribution
Correction factor is (1 R), where the
Sternheimer factor 0.25 < R < 0.35.
Valence Contribution
Quadrupole Splitting
The eigenvalues of the interaction Hamiltonian
are:

For
57
Fe The ground state (I = ) is
unperturbed
The excited state splits into two levels


( )
( ) ( )
2 1
2 2
2
3 1 1 3
1 2 4
/
I Q
/ I I m
I I
qQ e
E q + +

=
For
57
Fe the excited state splits into the two
levels 3/2, split by


and hence two lines in the same spectrum.
2 1
2
2
3 1
2
/
/
qQ e
q + = A
2 1
2
2
3 1
2
/
/
qQ e
q + = A
Electric Quadrupole Interaction
Figure
Electric Quadrupole Interaction

3/2
1/2 I=3/2
I=1/2
1/2
R
e
l
.

t
r
a
n
s
.

0
v(mm/s)
o

Example:
Fe
3+
3d
5
=> half-filled shell
therefore q
val
= 0
therefore is generally small and
temperature independent
Fe
2+
3d
6
=> half-filled shell + 3d
1

therefore q
val
0, dependent on
orbital occupancy therefore
generally large, and
temperature dependent

Magnetic Hyperfine Interaction
Hamiltonian


A nucleus with spin I interacts with a magnetic field H
to give eigenvalues

E
m
= -g
n

n
Bm
I

B . I g B . H

n n m

| = =
This splits the excited state (I = 3/2) into 4 and
the ground state (I = ) into 2.
The m
I
= 0,

1 selection rule gives 6
transitions and six line spectrum. The total
splitting depends on B
hf
the magnetic
hyperfine field at the nucleus.
Magnetic Hyperfine Interaction
Diagram
Magnetic Hyperfine Interaction
+3/2
-1/2
I=3/2
I=1/2
+1/2
-3/2
+1/2
-1/2
Sectrum
R
e
l
.

t
r
a
n
s
.

v(mm/s)
Magnetic Hyperfine Interaction
Examples
Fe
3+
(s = 5/2) B
hf
~ 50-60 T
Fe
2+
(s = 2) B
hf
~ 40-50 T
Iron Metal B
hf
~ 33T


The complete spectrum contains a
component for each type of iron atom
present.
% spectral intensity = % iron atoms of each
type (at T 0)
MSSBAUER SPECTRUM
Each component spectrum specified by:
isomer shift
quadrupole splitting
hyperfine field B
hf

linewidth
spectral area A


:


MSSBAUER SPECTRUM
Applications
Analysis, Chemistry, Magnetism, Solid State
Physics, Nuclear Physics, Biology, Medicine,
Earth Sciences, etc.