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Series of two lectures: MOSSBAUER SPECTROSCOPY

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 MöSSBAUER SPECTROSCOPY
Prof. (Dr.) S. DEVANARAYANAN,
Retired Prof. & Head, Department of Physics, University of Kerala, Kariavattom.
#2C, SFS-Fairmont, MP Appan Road, Vazhuthacaud, Thiruvananthapuram
<chsd1976@gmail.com>

“The true purpose of education is to train the mind to think.

For that reason it is priceless”. Albert Einstein

This Lecture [delivered for the “Refresher Course in Physics for College Teachers” at the
Academic Staff College, University of Kerala, Thiruvananthapuram, on 03, November 2011 is
dedicated to R.L. Mossbauer, NL (Born: 31 Jan 1929, Died: 14 Sep 2011)

1 INTRODUCTION

Mössbauer Spectroscopy is a technique based on the Mössbauer Effect, otherwise called Nuclear
Gamma ray Resonance (NGR) Spectroscopy. Take a look at the EM Spectrum for details on the
γ radiation. It is a phenomenon of Recoil-Free Resonant Emission and Absorption (interaction)
of γ -quanta with nuclei, embedded in solids, discovered by Rudolph L. Mössbauer, in 1957
[Nobel Prize in Physics, 1961]. This type of spectroscopy measures the transition energy between
allowed states of certain nuclei.
1.1 Applications:
1) Solid-state physics, 2) Surface physics, 3) Materials Science, 4) Chemistry,
5) Biochemistry, 6) Geology 7) Biology, 8) Medical Sciences and 9) Archeology. mainly using
compounds of 57 Fe and 119 Sn . There are about 45 different elements of the Periodic Table (Fig.
1), giving about 85 Mössbauer isotopes, for 105 Mössbauer transitions.

Fig 1: Elements of the Periodic Table of Elements which have known Mössbauer isotopes (shown
in red font)

Popular review [Eg. Devanarayanan, Mössbaue r Spectroscopy, J. Sci. Ind. Res. Vol 33, pp 222-
234, (1974)] and the very basic book [Eg. Wertheim, Mössbauer Spectroscopy (AP, NY, 1964]
on this subject.
.
1.2 Two major OBSTACLES to get Gamma ray Resonance (Mössbauer Effect):
a) The 'hyperfine' interactions between the nucleus and its environment are extremely small, b)
The recoil of the nucleus as the γ − ray is emitted or absorbed.

2.1 RECOIL OF FREE ATOMS

An energy quantum ( γ − radiation) gets emitted from a free (isolated) radioactive nuclide of
mass M ; it acquires a recoil energy, ER (Fig 2).

Fig 2: Recoil of free nuclei in emission or absorption of a gamma-ray

ER = Eγ2 . (2.1)
2M c 2
This much energy is removed from the nuclear transition energy, Et , of the emitting nuclide.
This results in the energy Eγ of the γ − radiation
Eγemitter = ( Et − ER ) (2.2)
Similarly an absorbing similar nucleus will recoil on absorption of Et , and effectively the
γ − radiation will have energy
Eγab = ( Et + ER ) (2.3)

2.2 THE DOPPLER EFFECT (Christian Andreas Doppler, 1845). If a moving source is
emitting waves of actual frequency f 0 , then an observer stationary relative to the medium detects
waves with a frequency f given by:
if the source moving away / toward observer,
V
f '= f S moving source (2.4)
(V ∓ v S )
∆λ = (V − vS ) / f S (2.5)
where V = the speed of sound. vS = the speed of the source
This is Doppler Effect.
 Fig 4. Another way of depicting Doppler shift.

2.3. The Doppler shift due to thermal motion of atoms. for Maxwell distribution of the speeds of
atoms, the emission and absorption lines also have a shape of Maxwell distribution (Gaussian)
with the Doppler width 2δ D
2δ D = 2 ER k BT eV (2.6)

γ − rays are in this region,

To produce a resonant signal the two energies need to overlap and this is shown in the BLACK-
shaded area. This area is extremely small, a millionth or less of the
and impractical as a technique.

Fig 6: Resonant overlap in free atoms. The overlap shown shaded is greatly exaggerated

2.4 NATURAL LINE WIDTH Γ ( ≡ Γ n ) OF γ − EMISSION AND ABSORPTION

A γ − ray is an extremely monochromatic energy quantum whose line broadening (width
Γ of nuclear level) is determined only by its lifetime τ ( ≡ τ m ) with the Heisenberg's Uncertainty
Principle ,
Γτ = ℏ . (2.7)
i.e., ∆ν = Γ n = 1 = 1
2π ∆t 2π τ m

The mean life τ m of the I = state in 57 Fe is τ = 1.4 x 10−7 s.. The energy distribution is given by
3
2
a Lorentzian (i.e., Breit-Wigner) profile (Fig. 7 ) with a FWHM (Full Width at Half Maximum)
of Γ nat = 4.7 x 10−9 eV ..
..
Comparison of different Monochromatic Lines:
 Fig. 7 Three different profiles of energy distributions

2.5. PROBABILITY f
Probability f is an important characteristic of the Mössbauer Effect. For a single atom
crystal with cubic symmetry the expression for f is

(2.8)
where = Average square displacement of atoms at the direction of emission of -quantum,
= Wavelength.
Factor f under room temperature has a comparably high value only for restricted number of
isotopes (( 57 Fe , 119 Sn , 181 Ta and some others) and depends on the temperature T of crystal.

2.6. THE REQUIRED 5 CONDITIONS TO OBSERVE THE MOSSBAUER EFFECT

a) The atom (ion, molecule, etc.) must be in the solid state, to avoid recoil and thermal
broadening.
b) The γ − ray energy Eγ ≈ Et must be fairly low (10 to 100 keV) to obtain an
appreciable number of recoil-less events
c) τ
The life times (mean life) of nuclear excited states giving rise to such γ − rays must
τ −6 −11
typically be in the range = 10 − 10 s , since longer lived nuclear species emit lines which
are extremely narrow for detection whereas the shorter lived species give lines which are broad
and get lost in the counting statistics.
d) The internal conversion electron coefficients α should be as small as possible ( α = 0 -
20), and
e) The absorber sample may have the Debye temperature, Θ D , preferably high.
Typical parameters for low Et values are listed in Table 1.

2.7. FAILURE OF -RAY RESONANCE IN GASES

Attempts of Mössbauer to observe -ray resonance in gases failed due to energy losses to
recoil, preventing resonance. The energy Eγ of emitted ray has Eγ < Et , but to be resonantly
absorbed it must be Eγ = ( Et + ER ) due to the recoil of the absorbing nucleus. To achieve
resonance the loss of the energy due to this must be overcome in some way. He was able to
observe resonance in solid Iodine, which raised the question of why ray resonance was possible
in solids, but not in gases. For a µ 3volume solid
ER ( Solid , µ 3volume) = ER ( Free atom) (2.9)
−15
ER (bound atom) ≅ 10 ER ( free atom) (2.10)
Mössbauer proposed that for the case of atoms embedded into a solid, under certain
circumstances, a fraction of the nuclear events could occur essentially without recoil. He
attributed the observed resonance to this recoil-free fraction of nuclear effects.

Fig 8: Recoil-free emission or absorption of a gamma-ray when the nuclei are in a solid

matrix
When the atoms are within a solid matrix the effective mass of the nucleus is very much greater.
The recoiling mass is now effectively the mass of the whole system, making ER and ED very
small. If the γ − ray energy is small enough the recoil of the nucleus is too low to be transmitted
as a phonon (vibration in the crystal lattice) and so the whole system recoils, making the recoil
energy practically zero a recoil-free event Eqn (2.10). That is why an emission (absorption)
spectrum represents a superposition of shifted line with Doppler width
2δ D = D = 2δ D = 2 ER k BT , at ( Et ± ER ) and non-shifted line with the width to be closed to
natural (Fig 9). In the case of free atoms,

δ D = Et v RMS c (2.11)
57
2.8. NUCLEAR PHYSICS OF Fe
The isotope with the strongest recoilless resonant absorption is 57 Fe (2.19% abundant
isotope of iron element). Since the vast majority of the work reported in the Mössbauer literature
is for iron, I restrict the present discussion to that isotope. Fig 10 shows the decay of 57 Fe from
its parent 57 Co . Of all the excited 57 Fe nuclei, about 10% will emit a 14.4 keV γ − ray via a
magnetic dipole transition from the metastable I = 32 state to I = 12 ground state ( I is the nuclear
spin). The ratio of recoil-free 14.4 keV photons to all the 14.4 keV photons emitted is f, the recoil-
free fraction of the source f varies with the properties of the solid and decreases monotonically
with increasing temperature.

57
Fig 10 Energy level scheme of Fe

2.9 HOW TO OBSERVE MOSSBAUER EFFECT?

To use a Mössbauer source as a spectroscopic tool one must be able to vary its energy
over a significant range. This is accomplished by Doppler shifting the energy of the gammabeam.
If v = frequency of γ rays, c = velocity of γ rays and v = relative velocity of the source and
the observer, frequency shift is
∆v = v v Hz (2.13)
c
Eγ = ( Et ± v ) eV (2.14)
c
Or, ∆Eγ = ( Eγ − Et ) = energy shift of the γ ray transition energy Et
 v Et
∆Eγ = ( Eγ − Et ) = eV (2.15)
c
Moving the source at a velocity of 1 mm s −1 toward the sample will increase the energy of the
photons by
14.4 keV (v / c) = 4.8 x 10
− 8
eV or ten (10) times natural line width, as. The " mm s −1 " is a
convenient Mössbauer unit.
.
3 EXPERIMENTAL SETUP

Basic Mossbauer Apparatus

a) Mössbauer Source: Mössbauer spectroscopy facilitates the study of minute energy changes
and hyperfine interactions which are otherwise undetectable. Full exploitation of this high
intrinsic resolution depends on the availability of sources which efficiently emit recoil-less
radiation of narrow line width, satisfying all the conditions mentioned earlier. They are available
commercially, either in one of the following matrices. 57 Co in Rh matrix 57 Co in Pd matrix
57
Co in Cu matrix , etc., from 5 to 200 mCi activity.
b) An absorber containing the appropriate nuclide, and
c) A suitable detector system for low energy γ − radiation. The detector can be a counter, a
scintillator counter [NaI (Tl) crystal], or a solid state detector, say a Ge(Li).
In order to observe resonance the source is mounted on an electro-mechanical transducer,
which works as a Doppler drive system, which is driven with a triangular wave, varying the
energy of the γ − rays according to
 v
Eγ = Et 1 ±  (2.14)
 c
Γn c
i.e., v= ≈ 1 mm s −1 (3.1)
Eγ
When a good spectrum is obtained, in the memory of the MCA (multi-channel analyzer),
it can be displayed in a CRO or read-out for analysis.
The apparatus is schematically shown as a block diagram in Fig. 13.

Fig. 13. The schematic diagram of a Mössbauer Spectrometer

Conventionally Mössbauer spectra are described as transmitted intensity (%) or counting rate in a
detector as a function of channel number or Doppler velocity, v. Distribution of registered
intensities is defined by a structure (shape) of Mössbauer lines. The spectrometer is calibrated
against a metallic iron foil and zero velocity is taken as the centroid of its room temperature
Mössbauer spectrum. In such a calibration spectrum, line widths of about 0.23 mm/s were
normally observed. The duration of a typical run is a few hours for non-biological compounds
and 24 hours for proteins

4. HYPERFINE INTERACTIONS

4.1 The interaction between a nucleus and its surrounding environment (i.e., the extra-nuclear
electrons) is known as a hyperfine interaction.
These interactions are very small compared to the energy levels of the nucleus itself, but
the extreme energy resolution of the Mössbauer effect enables these interactions to be observed.
The hyperfine interactions may shift energy levels or lift their degeneracy. Both of these
variations will affect the shape of a Mössbauer spectrum, as seen in the diagram.

4.1. Nuclear Hamiltonian can be expressed as

Hˆ = Hˆ 0 + E0 + M 1 + E2 + ... (4.1)
where Hˆ = all of the terms of the Hamiltonian other than the hyperfine interactions,
0
E = electric monopole interactions,
0
M = magnetic dipole interactions, and
1
E = electric quadrupole interactions.
2
These effects will be discussed in turn with reference to their physical causes and their
effects on the Mössbauer spectrum lineshapes and positions.

4.2. CENTRE OF SHIFT:

The Centre Shift (CS) of a Mössbauer spectrum, which sets the centroid of the spectrum, is
composed of two factors:
i) the Chemical Isomer Shift, , and
ii) the Second Order Doppler Effect (SODS), meaning that
CS = δ + SODS (4.2)
4.3. CHEMICAL ISOMER SHIFT ( CS = δ + SODS )
The Isomer Shift arises due to the non-zero volume of the nucleus and the electron charge
density due to electrons within it leading to an electric monopole (Coulomb) interaction which
alters the nuclear energy levels. The volume of the nucleus in its ground and excited states are
different and the electron densities are affected by the chemical environment. This relationship
between electron density (solid state factor) and nuclear radius (nuclear factor) is given by
2  2 2
δ = π Ze2 ψ s (0) E − ψ s (0)
A 
(< Re2 > − < Rg 2 >) (4.3)
3  

δ =
( )
Ze 2 R 2 c
5ε o Eγ ( )
{ρ (0)a − ρ (0) s }
∆R
R
mm s −1 (4.4)

where Rg2 = mean square radii of the ground nuclear state,

Re2 = mean square radii of the excited nuclear state,
2
ρ (0) E ≡ ψ S (0) E = electron density at the emitting nucleus,
2
ρ (0) A ≡ ψ S (0) A = electron density at the absorbing nucleus,
e = electronic charge,
R = effective nuclear radius,
c = velocity of light,
Eγ = energy of the Mössbauer gamma ray , ∆R = ( Re − Rg ) , and
Z= atomic number of the nucleus.
 57
Fig, 8 The Mossbauer spectrum of stainless steel using Co in Pd matrix

δ (Fe2+ ionic) > δ (Fe3+ ionic) > δ (Fe 2+ cov) > δ (Fe3+ cov) (4.5)

4.4. QUADRUPOLE SPITTING ( )

A nucleus that has a spin quantum number I > 12 has a non-spherical charge distribution.
The sign of Q indicates the shape of the deformation..
An asymmetric charge distribution around the nucleus causes an asymmetric electric field
at the nucleus, characterized by a tensor quantity viz., the Electric Field Gradient (EFG), ∇E . The
electric quadrupole interaction between these two quantities gives rise to a splitting in the nuclear
energy levels. The interaction between nuclear moment ( e Q ) and EFG ( ∇E ) is expressed by the
Hamiltonian,
where ∇E may be written as
∂ 2V
∇Ei j = − (4.7)
∂xi ∂x j

where Vis the electrostatic potential.

There are two contributions to the EFG;
i) lattice contributions from charges on distant ions and
ii) valence contributions due to incompletely filled electron shells. If a suitable coordinate system
is chosen the EFG can be represented by three principal axes, Vx x , Vy y and Vz z .. If an
asymmetry parameter is defined using these axes as

(4.8)
where Vx x ≥ Vy y ≥ Vz z so that 0 ≤ η ≤ 1 ,the EFG can be specified by two parameters: Vz z andη .
The excited state of 57
Fe has a spin I = 32 . The EFG has no effect on the I = 1
2
ground
state but does remove degeneracy in the excited state, splitting it into two sub-states mI = ± 12 and
mI = ± 32 , where the mI = ± 32 states are higher in energy for positive Vz z . (Fig 15)
 Fig 15: Quadrupole splitting for a 3/2 to 1/2 transition. The magnitude of quadrupole splitting,
∆ , is shown

Fig. 16 Schematic 57 Fe quadrupole split Mossbauer spectrum

The now non-degenerate excited states of 57 Fe give rise to a doublet in the Mössbauer
spectrum as illustrated in Fig 15 and Fig 16. The separation between the lines, , is known as
the Quadrupole Splitting and is given by
1
e2 q Q  η 2  2
∆= 1+
2  3 
(4.10)

which is a product of nuclear and solid state factors.

The line intensities are equal for polycrystalline samples. Texture or orientation effects can lead
to asymmetric doublets
The magnitude of Isomer shift δ and quadrupole splitting, are shown in Fig 17.
As the nuclear quadrupole moment is fixed the magnitude and sign of give
information about the sign of the EFG and magnitude ofη .

4.5. NUCLEAR ZEEMAN EFFECT

 Magnetic hyperfine splitting is caused by the dipole interaction between the nuclear spin

moment µ I and a magnetic field, Ĥ , ie, Zeeman splitting. The effective magnetic field
experienced by the nucleus is a combination of fields from the atom itself, from the lattice
through crystal field effects and from external applied fields. This can be considered for now as a

single field, called the internal field H , whose direction specifies the Principal Z-axis. The
n
Hamiltonian for the magnetic hyperfine dipole interaction is given as
   
Ĥ = − µ I i H = - g I µ N I i H (4.12)

where µ N = the Nuclear Magneton , ( µ I = the nuclear magnetic moment, I = the nuclear spin
and g I = the nuclear g -factor.
Energy of the non-degenerate level are:

EM = - g I µ N H mI (4.13)

where mI is the magnetic quantum number representing the z-component of I (i.e.,
mI = ± I , ±( I − 1),... ). Expression (4.13) is a product a nuclear factor and a solid state factor.
The magnetic field splits the nuclear level for spin (2 I + 1) equi-spaced non-
>0 into
degenerate substates. This and the selection rule of ∆mI = 0, ±1 produces splitting and a
resultant spectrum. For example, the 57 Fe ground state I =1/2 splits into two, and excited state
I = 3 splits into four. The selection rule of ∆mI = 0, ± 1 gives six possible transitions.(six
2
finger pattern) of 57 Fe . as shown in Fig 18 for a 3 → 1 transition.
2 2
 Fig 18: Magnetic splitting of the nuclear energy levels

The splitting is directly proportional to the magnetic field applied and so Mössbauer technique
provides a way of measuring it.
4.6. COMBINED MAGNETIC AND QUADRIPOLE INTERACTIONS for 57 Fe
giving a spectrum as in Fig.20.

57
Fig.20: The effect of a first-order quadrupole perturbation on a Fe magnetic hyperfine
57
spectrum for a Fe 3 → 1
2 2
transition.Lines 2, 3, 4, 5 are shifted relative to lines 1, 6.

5.. ANALYSIS OF SPECTRA

 At first the spectrometer is calibrated by taking the spectrum of a standard material for
comparison. A spectrum of the substance under study is taken. The final analysis of the
sufficiently treated spectrum, in terms of hyperfine interactions is made by using a suitable
computer program in a PC, which provides the values for the Mossbauer parameters for a
complex spectrum.

6. CONCLUSION
The Mössbauer Effect was a great discovery in Physics, and opened up new ways to
study solid materials. It was developed as a peculiar method of spectroscopy, utilizing the nuclear
hyperfine structure, and its application has been extended to not only in the field of Materials
Science but also Mineralogy, Geology, Biology, Medical science, Environmental science and
even Archeology. Such an expansion from fundamental physics to various applications may be
compared with that of NMR (which was born twelve years earlier than then the Mössbauer
Effect) and also utilizes the hyperfine interactions, and also may be compared with that of the
Raman Effect. It is noticeable that as in the case of the NMR and Raman and the Infrared types of
spectroscopy, without technical developments, its rapid and wide application would not have
been achieved.

Books
1) Mössbauer Spectroscopy and its Applications, T E Cranshaw, B W Dale, G O Longworth and
C E Johnson, (Cambridge Univ. Press: Cambridge) 1985
2) Mössbauer Spectroscopy, D P E Dickson and F J Berry, (Cambridge Univ. Press: Cambridge)
1986
3) The Mössbauer Effect, H Frauenfelder, (Benjamin: New York) 1962
4) Principles of Mössbauer Spectroscopy, T C Gibb, (Chapman and Hall: London) 1977
5) Mössbauer Spectroscopy, N N Greenwood and T C Gibb, (Chapman and Hall: London) 1971
6) Chemical Applications of Mössbauer Spectroscopy, V I Goldanskii and R H Herber ed.,
(Academic Press Inc: London) 1968.
7) An Introduction to Mossbauer Spectroscopy, Mauy, Leopold, (Plenum Press, NY,) 1971
8) Mossbauer Effect and Its Applications, Bhide, VG, (TMH, New Delhi) 1973.
9) Mössbauer Spectroscopy Applied to Inorganic Chemistry Vols. 1-3, G J Long, ed., (Plenum:
New York) 1984-1989.
10) Mössbauer Spectroscopy Applied to Magnetism and Materials Science Vol. 1, G J Long and
F Grandjean, eds., (Plenum: New York) 1993
11) Wertheim,GK., Mossbauer Spectroscopy (AP, NY, 1964].
12) Devanarayanan, S., Mossbaue r Spectroscopy, J. Sci. Ind. Res. Vol 33, pp 222- 234, (1974)].
13) Mössbauer, R. L. (1958). "Kernresonanzfluoreszenz von Gammastrahlung in Ir191" (in
German). Zeitschrift für Physik A 151 (2): 124–143.
14) Frauenfelder, H. (1962). The Mössbauer Effect. W. A. Benjamin.
15) Eyges, L. (1965). "Physics of the Mössbauer Effect". American Journal of Physics 33 (10):
790–802.
16) Hesse, J. (1973). "Simple Arrangement for Educational Mössbauer-Effect Measurements".
American Journal of Physics 41: 127–129.
17) Ninio, F. (1973). "The Forced Harmonic Oscillator and the Zero-Phonon Transition of the
Mössbauer Effect". American Journal of Physics 41 (5): 648–649.
18) Vandergrift, G.; Fultz, B. (1998). "The Mössbauer effect explained". American Journal of
Physics 66 (7): 593–596.
 MöSSBAUER SPECTROSCOPY
Prof. (Dr.) S. DEVANARAYANAN,
Retired Prof. & Head, Department of Physics, University of Kerala, Kariavattom.
#2C, SFS-Fairmont, MP Appan Road, Vazhuthacaud, Thiruvananthapuram
<chsd1976@gmail.com>

“The true purpose of education is to train the mind to think.

For that reason it is priceless”. Albert Einstein

This Lecture [delivered for the “Refresher Course in Physics for College Teachers” at the
Academic Staff College, University of Kerala, Thiruvananthapuram, on 03, November 2011 is
dedicated to R.L. Mossbauer, NL (Born: 31 Jan 1929, Died: 14 Sep 2011)

1 INTRODUCTION

Mössbauer Spectroscopy is a technique based on the Mössbauer Effect, otherwise called Nuclear
Gamma ray Resonance (NGR) Spectroscopy. Take a look at the EM Spectrum for details on the
γ radiation. It is a phenomenon of Recoil-Free Resonant Emission and Absorption (interaction)
of γ -quanta with nuclei, embedded in solids, discovered by Rudolph L. Mössbauer, in 1957
[Nobel Prize in Physics, 1961]. This type of spectroscopy measures the transition energy between
allowed states of certain nuclei.
1.1 Applications:
1) Solid-state physics, 2) Surface physics, 3) Materials Science, 4) Chemistry,
5) Biochemistry, 6) Geology 7) Biology, 8) Medical Sciences and 9) Archeology. mainly using
compounds of 57 Fe and 119 Sn . There are about 45 different elements of the Periodic Table (Fig.
1), giving about 85 Mössbauer isotopes, for 105 Mössbauer transitions.

Fig 1: Elements of the Periodic Table of Elements which have known Mössbauer isotopes (shown
in red font)

Popular review [Eg. Devanarayanan, Mössbaue r Spectroscopy, J. Sci. Ind. Res. Vol 33, pp 222-
234, (1974)] and the very basic book [Eg. Wertheim, Mössbauer Spectroscopy (AP, NY, 1964]
on this subject.
.
1.2 Two major OBSTACLES to get Gamma ray Resonance (Mössbauer Effect):
a) The 'hyperfine' interactions between the nucleus and its environment are extremely small, b)
The recoil of the nucleus as the γ − ray is emitted or absorbed.

2.1 RECOIL OF FREE ATOMS

An energy quantum ( γ − radiation) gets emitted from a free (isolated) radioactive nuclide of
mass M ; it acquires a recoil energy, ER (Fig 2).

Fig 2: Recoil of free nuclei in emission or absorption of a gamma-ray

ER = Eγ2 . (2.1)
2M c 2
This much energy is removed from the nuclear transition energy, Et , of the emitting nuclide.
This results in the energy Eγ of the γ − radiation
Eγemitter = ( Et − ER ) (2.2)
Similarly an absorbing similar nucleus will recoil on absorption of Et , and effectively the
γ − radiation will have energy
Eγab = ( Et + ER ) (2.3)

2.2 THE DOPPLER EFFECT (Christian Andreas Doppler, 1845). If a moving source is
emitting waves of actual frequency f 0 , then an observer stationary relative to the medium detects
waves with a frequency f given by:
if the source moving away / toward observer,
V
f '= f S moving source (2.4)
(V ∓ v S )
∆λ = (V − vS ) / f S (2.5)
where V = the speed of sound. vS = the speed of the source
This is Doppler Effect.
 Fig 4. Another way of depicting Doppler shift.

2.3. The Doppler shift due to thermal motion of atoms. for Maxwell distribution of the speeds of
atoms, the emission and absorption lines also have a shape of Maxwell distribution (Gaussian)
with the Doppler width 2δ D
2δ D = 2 ER k BT eV (2.6)

γ − rays are in this region,

To produce a resonant signal the two energies need to overlap and this is shown in the BLACK-
shaded area. This area is extremely small, a millionth or less of the
and impractical as a technique.

Fig 6: Resonant overlap in free atoms. The overlap shown shaded is greatly exaggerated

2.4 NATURAL LINE WIDTH Γ ( ≡ Γ n ) OF γ − EMISSION AND ABSORPTION

A γ − ray is an extremely monochromatic energy quantum whose line broadening (width
Γ of nuclear level) is determined only by its lifetime τ ( ≡ τ m ) with the Heisenberg's Uncertainty
Principle ,
Γτ = ℏ . (2.7)
i.e., ∆ν = Γ n = 1 = 1
2π ∆t 2π τ m

The mean life τ m of the I = state in 57 Fe is τ = 1.4 x 10−7 s.. The energy distribution is given by
3
2
a Lorentzian (i.e., Breit-Wigner) profile (Fig. 7 ) with a FWHM (Full Width at Half Maximum)
of Γ nat = 4.7 x 10−9 eV ..
..
Comparison of different Monochromatic Lines:
 Fig. 7 Three different profiles of energy distributions

2.5. PROBABILITY f
Probability f is an important characteristic of the Mössbauer Effect. For a single atom
crystal with cubic symmetry the expression for f is

(2.8)
where = Average square displacement of atoms at the direction of emission of -quantum,
= Wavelength.
Factor f under room temperature has a comparably high value only for restricted number of
isotopes (( 57 Fe , 119 Sn , 181 Ta and some others) and depends on the temperature T of crystal.

2.6. THE REQUIRED 5 CONDITIONS TO OBSERVE THE MOSSBAUER EFFECT

a) The atom (ion, molecule, etc.) must be in the solid state, to avoid recoil and thermal
broadening.
b) The γ − ray energy Eγ ≈ Et must be fairly low (10 to 100 keV) to obtain an
appreciable number of recoil-less events
c) τ
The life times (mean life) of nuclear excited states giving rise to such γ − rays must
τ −6 −11
typically be in the range = 10 − 10 s , since longer lived nuclear species emit lines which
are extremely narrow for detection whereas the shorter lived species give lines which are broad
and get lost in the counting statistics.
d) The internal conversion electron coefficients α should be as small as possible ( α = 0 -
20), and
e) The absorber sample may have the Debye temperature, Θ D , preferably high.
Typical parameters for low Et values are listed in Table 1.

2.7. FAILURE OF -RAY RESONANCE IN GASES

Attempts of Mössbauer to observe -ray resonance in gases failed due to energy losses to
recoil, preventing resonance. The energy Eγ of emitted ray has Eγ < Et , but to be resonantly
absorbed it must be Eγ = ( Et + ER ) due to the recoil of the absorbing nucleus. To achieve
resonance the loss of the energy due to this must be overcome in some way. He was able to
observe resonance in solid Iodine, which raised the question of why ray resonance was possible
in solids, but not in gases. For a µ 3volume solid
ER ( Solid , µ 3volume) = ER ( Free atom) (2.9)
−15
ER (bound atom) ≅ 10 ER ( free atom) (2.10)
Mössbauer proposed that for the case of atoms embedded into a solid, under certain
circumstances, a fraction of the nuclear events could occur essentially without recoil. He
attributed the observed resonance to this recoil-free fraction of nuclear effects.

Fig 8: Recoil-free emission or absorption of a gamma-ray when the nuclei are in a solid

matrix
When the atoms are within a solid matrix the effective mass of the nucleus is very much greater.
The recoiling mass is now effectively the mass of the whole system, making ER and ED very
small. If the γ − ray energy is small enough the recoil of the nucleus is too low to be transmitted
as a phonon (vibration in the crystal lattice) and so the whole system recoils, making the recoil
energy practically zero a recoil-free event Eqn (2.10). That is why an emission (absorption)
spectrum represents a superposition of shifted line with Doppler width
2δ D = D = 2δ D = 2 ER k BT , at ( Et ± ER ) and non-shifted line with the width to be closed to
natural (Fig 9). In the case of free atoms,

δ D = Et v RMS c (2.11)
57
2.8. NUCLEAR PHYSICS OF Fe
The isotope with the strongest recoilless resonant absorption is 57 Fe (2.19% abundant
isotope of iron element). Since the vast majority of the work reported in the Mössbauer literature
is for iron, I restrict the present discussion to that isotope. Fig 10 shows the decay of 57 Fe from
its parent 57 Co . Of all the excited 57 Fe nuclei, about 10% will emit a 14.4 keV γ − ray via a
magnetic dipole transition from the metastable I = 32 state to I = 12 ground state ( I is the nuclear
spin). The ratio of recoil-free 14.4 keV photons to all the 14.4 keV photons emitted is f, the recoil-
free fraction of the source f varies with the properties of the solid and decreases monotonically
with increasing temperature.

57
Fig 10 Energy level scheme of Fe

2.9 HOW TO OBSERVE MOSSBAUER EFFECT?

To use a Mössbauer source as a spectroscopic tool one must be able to vary its energy
over a significant range. This is accomplished by Doppler shifting the energy of the gammabeam.
If v = frequency of γ rays, c = velocity of γ rays and v = relative velocity of the source and
the observer, frequency shift is
∆v = v v Hz (2.13)
c
Eγ = ( Et ± v ) eV (2.14)
c
Or, ∆Eγ = ( Eγ − Et ) = energy shift of the γ ray transition energy Et
 v Et
∆Eγ = ( Eγ − Et ) = eV (2.15)
c
Moving the source at a velocity of 1 mm s −1 toward the sample will increase the energy of the
photons by
14.4 keV (v / c) = 4.8 x 10
− 8
eV or ten (10) times natural line width, as. The " mm s −1 " is a
convenient Mössbauer unit.
.
3 EXPERIMENTAL SETUP

Basic Mossbauer Apparatus

a) Mössbauer Source: Mössbauer spectroscopy facilitates the study of minute energy changes
and hyperfine interactions which are otherwise undetectable. Full exploitation of this high
intrinsic resolution depends on the availability of sources which efficiently emit recoil-less
radiation of narrow line width, satisfying all the conditions mentioned earlier. They are available
commercially, either in one of the following matrices. 57 Co in Rh matrix 57 Co in Pd matrix
57
Co in Cu matrix , etc., from 5 to 200 mCi activity.
b) An absorber containing the appropriate nuclide, and
c) A suitable detector system for low energy γ − radiation. The detector can be a counter, a
scintillator counter [NaI (Tl) crystal], or a solid state detector, say a Ge(Li).
In order to observe resonance the source is mounted on an electro-mechanical transducer,
which works as a Doppler drive system, which is driven with a triangular wave, varying the
energy of the γ − rays according to
 v
Eγ = Et 1 ±  (2.14)
 c
Γn c
i.e., v= ≈ 1 mm s −1 (3.1)
Eγ
When a good spectrum is obtained, in the memory of the MCA (multi-channel analyzer),
it can be displayed in a CRO or read-out for analysis.
The apparatus is schematically shown as a block diagram in Fig. 13.

Fig. 13. The schematic diagram of a Mössbauer Spectrometer

Conventionally Mössbauer spectra are described as transmitted intensity (%) or counting rate in a
detector as a function of channel number or Doppler velocity, v. Distribution of registered
intensities is defined by a structure (shape) of Mössbauer lines. The spectrometer is calibrated
against a metallic iron foil and zero velocity is taken as the centroid of its room temperature
Mössbauer spectrum. In such a calibration spectrum, line widths of about 0.23 mm/s were
normally observed. The duration of a typical run is a few hours for non-biological compounds
and 24 hours for proteins

4. HYPERFINE INTERACTIONS

4.1 The interaction between a nucleus and its surrounding environment (i.e., the extra-nuclear
electrons) is known as a hyperfine interaction.
These interactions are very small compared to the energy levels of the nucleus itself, but
the extreme energy resolution of the Mössbauer effect enables these interactions to be observed.
The hyperfine interactions may shift energy levels or lift their degeneracy. Both of these
variations will affect the shape of a Mössbauer spectrum, as seen in the diagram.

4.1. Nuclear Hamiltonian can be expressed as

Hˆ = Hˆ 0 + E0 + M 1 + E2 + ... (4.1)
where Hˆ = all of the terms of the Hamiltonian other than the hyperfine interactions,
0
E = electric monopole interactions,
0
M = magnetic dipole interactions, and
1
E = electric quadrupole interactions.
2
These effects will be discussed in turn with reference to their physical causes and their
effects on the Mössbauer spectrum lineshapes and positions.

4.2. CENTRE OF SHIFT:

The Centre Shift (CS) of a Mössbauer spectrum, which sets the centroid of the spectrum, is
composed of two factors:
i) the Chemical Isomer Shift, , and
ii) the Second Order Doppler Effect (SODS), meaning that
CS = δ + SODS (4.2)
4.3. CHEMICAL ISOMER SHIFT ( CS = δ + SODS )
The Isomer Shift arises due to the non-zero volume of the nucleus and the electron charge
density due to electrons within it leading to an electric monopole (Coulomb) interaction which
alters the nuclear energy levels. The volume of the nucleus in its ground and excited states are
different and the electron densities are affected by the chemical environment. This relationship
between electron density (solid state factor) and nuclear radius (nuclear factor) is given by
2  2 2
δ = π Ze2 ψ s (0) E − ψ s (0)
A 
(< Re2 > − < Rg 2 >) (4.3)
3  

δ =
( )
Ze 2 R 2 c
5ε o Eγ ( )
{ρ (0)a − ρ (0) s }
∆R
R
mm s −1 (4.4)

where Rg2 = mean square radii of the ground nuclear state,

Re2 = mean square radii of the excited nuclear state,
2
ρ (0) E ≡ ψ S (0) E = electron density at the emitting nucleus,
2
ρ (0) A ≡ ψ S (0) A = electron density at the absorbing nucleus,
e = electronic charge,
R = effective nuclear radius,
c = velocity of light,
Eγ = energy of the Mössbauer gamma ray , ∆R = ( Re − Rg ) , and
Z= atomic number of the nucleus.
 57
Fig, 8 The Mossbauer spectrum of stainless steel using Co in Pd matrix

δ (Fe2+ ionic) > δ (Fe3+ ionic) > δ (Fe 2+ cov) > δ (Fe3+ cov) (4.5)

4.4. QUADRUPOLE SPITTING ( )

A nucleus that has a spin quantum number I > 12 has a non-spherical charge distribution.
The sign of Q indicates the shape of the deformation..
An asymmetric charge distribution around the nucleus causes an asymmetric electric field
at the nucleus, characterized by a tensor quantity viz., the Electric Field Gradient (EFG), ∇E . The
electric quadrupole interaction between these two quantities gives rise to a splitting in the nuclear
energy levels. The interaction between nuclear moment ( e Q ) and EFG ( ∇E ) is expressed by the
Hamiltonian,
where ∇E may be written as
∂ 2V
∇Ei j = − (4.7)
∂xi ∂x j

where Vis the electrostatic potential.

There are two contributions to the EFG;
i) lattice contributions from charges on distant ions and
ii) valence contributions due to incompletely filled electron shells. If a suitable coordinate system
is chosen the EFG can be represented by three principal axes, Vx x , Vy y and Vz z .. If an
asymmetry parameter is defined using these axes as

(4.8)
where Vx x ≥ Vy y ≥ Vz z so that 0 ≤ η ≤ 1 ,the EFG can be specified by two parameters: Vz z andη .
The excited state of 57
Fe has a spin I = 32 . The EFG has no effect on the I = 1
2
ground
state but does remove degeneracy in the excited state, splitting it into two sub-states mI = ± 12 and
mI = ± 32 , where the mI = ± 32 states are higher in energy for positive Vz z . (Fig 15)
 Fig 15: Quadrupole splitting for a 3/2 to 1/2 transition. The magnitude of quadrupole splitting,
∆ , is shown

Fig. 16 Schematic 57 Fe quadrupole split Mossbauer spectrum

The now non-degenerate excited states of 57 Fe give rise to a doublet in the Mössbauer
spectrum as illustrated in Fig 15 and Fig 16. The separation between the lines, , is known as
the Quadrupole Splitting and is given by
1
e2 q Q  η 2  2
∆= 1+
2  3 
(4.10)

which is a product of nuclear and solid state factors.

The line intensities are equal for polycrystalline samples. Texture or orientation effects can lead
to asymmetric doublets
The magnitude of Isomer shift δ and quadrupole splitting, are shown in Fig 17.
As the nuclear quadrupole moment is fixed the magnitude and sign of give
information about the sign of the EFG and magnitude ofη .

4.5. NUCLEAR ZEEMAN EFFECT

 Magnetic hyperfine splitting is caused by the dipole interaction between the nuclear spin

moment µ I and a magnetic field, Ĥ , ie, Zeeman splitting. The effective magnetic field
experienced by the nucleus is a combination of fields from the atom itself, from the lattice
through crystal field effects and from external applied fields. This can be considered for now as a

single field, called the internal field H , whose direction specifies the Principal Z-axis. The
n
Hamiltonian for the magnetic hyperfine dipole interaction is given as
   
Ĥ = − µ I i H = - g I µ N I i H (4.12)

where µ N = the Nuclear Magneton , ( µ I = the nuclear magnetic moment, I = the nuclear spin
and g I = the nuclear g -factor.
Energy of the non-degenerate level are:

EM = - g I µ N H mI (4.13)

where mI is the magnetic quantum number representing the z-component of I (i.e.,
mI = ± I , ±( I − 1),... ). Expression (4.13) is a product a nuclear factor and a solid state factor.
The magnetic field splits the nuclear level for spin (2 I + 1) equi-spaced non-
>0 into
degenerate substates. This and the selection rule of ∆mI = 0, ±1 produces splitting and a
resultant spectrum. For example, the 57 Fe ground state I =1/2 splits into two, and excited state
I = 3 splits into four. The selection rule of ∆mI = 0, ± 1 gives six possible transitions.(six
2
finger pattern) of 57 Fe . as shown in Fig 18 for a 3 → 1 transition.
2 2
 Fig 18: Magnetic splitting of the nuclear energy levels

The splitting is directly proportional to the magnetic field applied and so Mössbauer technique
provides a way of measuring it.
4.6. COMBINED MAGNETIC AND QUADRIPOLE INTERACTIONS for 57 Fe
giving a spectrum as in Fig.20.

57
Fig.20: The effect of a first-order quadrupole perturbation on a Fe magnetic hyperfine
57
spectrum for a Fe 3 → 1
2 2
transition.Lines 2, 3, 4, 5 are shifted relative to lines 1, 6.

5.. ANALYSIS OF SPECTRA

 At first the spectrometer is calibrated by taking the spectrum of a standard material for
comparison. A spectrum of the substance under study is taken. The final analysis of the
sufficiently treated spectrum, in terms of hyperfine interactions is made by using a suitable
computer program in a PC, which provides the values for the Mossbauer parameters for a
complex spectrum.

6. CONCLUSION
The Mössbauer Effect was a great discovery in Physics, and opened up new ways to
study solid materials. It was developed as a peculiar method of spectroscopy, utilizing the nuclear
hyperfine structure, and its application has been extended to not only in the field of Materials
Science but also Mineralogy, Geology, Biology, Medical science, Environmental science and
even Archeology. Such an expansion from fundamental physics to various applications may be
compared with that of NMR (which was born twelve years earlier than then the Mössbauer
Effect) and also utilizes the hyperfine interactions, and also may be compared with that of the
Raman Effect. It is noticeable that as in the case of the NMR and Raman and the Infrared types of
spectroscopy, without technical developments, its rapid and wide application would not have
been achieved.

Books
1) Mössbauer Spectroscopy and its Applications, T E Cranshaw, B W Dale, G O Longworth and
C E Johnson, (Cambridge Univ. Press: Cambridge) 1985
2) Mössbauer Spectroscopy, D P E Dickson and F J Berry, (Cambridge Univ. Press: Cambridge)
1986
3) The Mössbauer Effect, H Frauenfelder, (Benjamin: New York) 1962
4) Principles of Mössbauer Spectroscopy, T C Gibb, (Chapman and Hall: London) 1977
5) Mössbauer Spectroscopy, N N Greenwood and T C Gibb, (Chapman and Hall: London) 1971
6) Chemical Applications of Mössbauer Spectroscopy, V I Goldanskii and R H Herber ed.,
(Academic Press Inc: London) 1968.
7) An Introduction to Mossbauer Spectroscopy, Mauy, Leopold, (Plenum Press, NY,) 1971
8) Mossbauer Effect and Its Applications, Bhide, VG, (TMH, New Delhi) 1973.
9) Mössbauer Spectroscopy Applied to Inorganic Chemistry Vols. 1-3, G J Long, ed., (Plenum:
New York) 1984-1989.
10) Mössbauer Spectroscopy Applied to Magnetism and Materials Science Vol. 1, G J Long and
F Grandjean, eds., (Plenum: New York) 1993
11) Wertheim,GK., Mossbauer Spectroscopy (AP, NY, 1964].
12) Devanarayanan, S., Mossbaue r Spectroscopy, J. Sci. Ind. Res. Vol 33, pp 222- 234, (1974)].
13) Mössbauer, R. L. (1958). "Kernresonanzfluoreszenz von Gammastrahlung in Ir191" (in
German). Zeitschrift für Physik A 151 (2): 124–143.
14) Frauenfelder, H. (1962). The Mössbauer Effect. W. A. Benjamin.
15) Eyges, L. (1965). "Physics of the Mössbauer Effect". American Journal of Physics 33 (10):
790–802.
16) Hesse, J. (1973). "Simple Arrangement for Educational Mössbauer-Effect Measurements".
American Journal of Physics 41: 127–129.
17) Ninio, F. (1973). "The Forced Harmonic Oscillator and the Zero-Phonon Transition of the
Mössbauer Effect". American Journal of Physics 41 (5): 648–649.
18) Vandergrift, G.; Fultz, B. (1998). "The Mössbauer effect explained". American Journal of
Physics 66 (7): 593–596.

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