Mossbauer Spectros

MÖSSBAUER SPECTROSCOPY
Mössbauer spectroscopy is concerned with transitions between energy levels within the nuclei of atoms. It
Lecture notes: Dr. Cyriac Mathew
was discovered by Rudolph Mössbauer who was awarded Nobel prize for physics in 1961. About a third of the
known elements, mainly the heavier ones, when formed by the radioactive decay of an isotope of the same or a
different element, are initially produced in an excited nuclear state. After a very short delay (of the order of
microseconds) the excited nucleus reverts to the ground state and emits energy of a very high frequency, usually in
the -ray region of the spectrum. It is the study of this -ray emission and subsequent reabsorption constitutes
the Mössbauer or -ray spectroscopy. It is also referred as the ‘Mössbauer Effect’. Mössbauer spectroscopy is a
versatile technique that can be used to provide information in many areas of science such as Physics, Chemistry,
Biology and Metallurgy. It can give very precise information about the chemical, structural, magnetic and time-
dependent properties of a material.
The Mössbauer Effect
For many years it was recognised that the gamma rays emitted when radioactive nuclei in excited states
decay, might excite other stable nuclei of the same isotope. This must give rise to nuclear resonant absorption and
fluorescence. However, initial attempts to detect these resonant processes were unsuccessful mainly because of the
nuclear recoil, which accompanies both the emission and absorption of the gamma ray by a free nucleus. As a result
of this nuclear recoil the energy of the emitted gamma ray is less than the energy difference between the two
nuclear levels. If resonant absorption is to occur the energy of the incoming gamma ray needs to be greater than this
energy difference. Thus, for free nuclei the recoil energy prevents resonant absorption of gamma rays under normal
circumstances.
Lectrue notes Dr. Cyriac Mathew
The Mössbauer effect states that when some atoms are held tightly in crystalline atomic structures, the
gamma radiation emitted by their nuclei are very close to being recoil-free. This implies that the emitted photon has
the exact frequency that corresponds to the transition energy between the nuclear ground state and the excited
state. When this photon carrying the full nuclear transition
Nuclear excited state Nuclear excited state
energy, strikes another similar nucleus, which also is
Lecture notes : Dr. Cyriac Mathew Lecture notes: Dr. Cyriac Mathew Lecture notes: Dr. Cyriac Mathew
embedded in a tight crystalline structure, absorption may

occur. Because the nuclear energy levels are very sharply
defined, only such a photon - one that carries the exact
transition energy - may excite another nucleus (of course,
only if absorber doesn't recoil either). A simple schematic
picture is shown in Fig. 1.
The energy levels of a nucleus situated in an atom Ground state Ground state
and in a solid are modified by the environment of the
Source Absorber
nucleus. Mössbauer spectroscopy is a technique which
Fig. 1
enables these energy levels to be investigated by measuring
the energy dependence of the resonant absorption of Mössbauer gamma rays by nuclei. This is possible since the
recoil-free processes arising from the Mössbauer effect lead to the resonant absorption of gamma rays with an
extremely precise energy. This enables the very small energy changes resulting from the hyperfine interactions
between the nucleus and its surrounding electrons to be investigated and therefore Mössbauer spectroscopy
provides a means of using the nucleus as a probe of its environment.
Mössbauer effect has now been detected in over one hundred isotopes, but 57Fe is the most widely used
isotope, especially in iron containing systems. The most common experimental arrangement for Mössbauer
spectroscopy involves a radioactive source containing the Mössbauer isotope in an excited state and an absorber
1
consisting of the material to be investigated which contains this same isotope in its ground state. For example, the
source for 57Fe Mössbauer spectroscopy is normally radioactive 57Co which is a relatively long-lived species, having a
half-life of some 270 days. It undergoes a spontaneous electron capture transition to give a metastable state of 57Fe
(57Fe*) which in turn decays to the ground state via a gamma ray emission which includes the 14.4 keV Mössbauer
gamma ray. Fig. 2.
57 The radioactive source nuclei are usually embedded in

Co
a matrix which provides the necessary solid environment as
well as giving the simplest possible hyperfine interaction

between these nuclei and their environment. In the normal
transmission experiment the gamma rays emitted by the
Electron capture source pass through the absorber, where they may be partially
absorbed, and they then pass to a suitable detector. In order
t1/2 =270 days

to investigate the energy levels of the Mössbauer nucleus in
the absorber it is necessary to modify the energy of the
gamma rays emitted by the source so that they can have the
57 correct energy for resonant absorption. This is usually
Fe*
accomplished by moving the source relative to a stationary
Gamma rays absorber, and hence giving the gamma rays an energy shift as
E a result of the Doppler effect1. The motion of the source is
t1/2 =1.5 x 10−7s normally oscillatory in order to provide an energy scan.
57
Fe Fig. 3 shows a schematic representation of Mössbauer
Fig. 2 spectroscopy. It represents the simplest case where the source

and absorber nuclei are in identical environments. It shows a
Mössbauer spectrum where emission and absorption occur at the same gamma ray frequency. Therefore, the
spectral line occurs at zero velocity.
Excited state
Gamma ray
counts
detector
velocity
Ground state
0
Emitter nucleus Absorber nucleus
Fig. 3
In the example shown above the cobalt nucleus is seen to produce 57Fe in an excited energy state following
electron capture, designated as 57Fe*. 57Fe* very rapidly drops to the ground state 57Fe. Now if a second 57Fe nucleus,
initially in the ground state, were to be put in the emitted radiation beam, it would be expected to absorb energy
1
The Doppler effect (or the Doppler shift) is the change in frequency of a wave in relation to an observer who is moving relative
to the wave source. The Doppler effect causes the received frequency of a source (how it is perceived when it gets to its
destination) to differ from the sent frequency if there is motion that is increasing or decreasing the distance between the source
and the receiver. A common example of Doppler shift is the change of pitch heard when a vehicle sounding a horn approaches
and recedes from an observer. Compared to the emitted frequency, the received frequency is higher during the approach,
identical at the instant of passing by, and lower during the recession.
2
from the beam and to become excited into the 57Fe* state. A -ray detector (a scintillator or a Geiger counter) placed
in the beam behind the absorber should show that this has happened. In fact, it was found possible to observe -ray
absorption only if the source material were moved relative to the sample.
Isomer shift (or chemical shift)
The nucleus is not a point charge. It has a finite radius and has a non-zero volume. In most cases the excited
and ground states have different radii. Because of the electrostatic interaction of the nucleus with the electric field
due to orbital electrons (mainly s-electrons which has finite probability within the nucleus) the nuclear energy levels
are slightly different in atoms of different compounds. The isomer shift of the absorption lines in the Mössbauer
spectrum is a result of the electrostatic interaction between the nuclear charge distribution over the finite nuclear
volume and the electronic charge density over this volume. This shift arises because of the difference in the nuclear
volume of the ground and excited states, and also due to the difference between the electron densities at the
Mössbauer nuclei in different materials. This shifts the whole spectrum positively or negatively depending upon the
s-electron density.
The isomer shift is useful for determining valency states, ligand bonding states, electron shielding and the
electron-drawing power of electronegative groups. For example, the electron configurations for Fe 2+ and Fe3+ are
(3d)6 and (3d)5 respectively. The ferrous ions have less s-electron density at the nucleus due to the greater screening
of the d-electrons. Thus, ferrous ions have larger positive isomer shifts than ferric ions.
Excited state
counts

− 0 +
velocity
Ground state Nucleus in sample

Isolated nucleus material
Fig. 4
Quadrupole splitting
Nuclei in states with a nuclear spin angular momentum quantum number I > ½ have non-spherical charge
distribution. This give rise to the nuclear quadrupole moment. When the nuclear quadrupole moment experiences
an asymmetric electric field, quadrupole interaction occurs which give rise to a splitting of the nuclear energy levels.
The asymmetric electric field is produced by an asymmetric charge distribution of electrons or due to ligands
surrounding the atom. Isotopes such as 57Fe and 119Sn, the excited state have I =3/2 and the excited states split into
mI =  ½ and mI =  3/2. This give rise to a two-line spectrum or doublet. The magnitude of the quadrupole splitting
is represented by . The splitting is shown in Fig. 5.
3
The quadrupole splitting observed in a system reflects the symmetry of the bonding environment and the
local structure in the vicinity of the Mössbauer atom. Valuable information can be obtained by comparing
quadrupole splitting data obtained from related materials, and this can be particularly informative when the data are
considered in conjunction with data on the isomer shifts. Quadrupole splitting data can give information relating to
mI = 3/2

I = 3/2 mI = 1/2
counts
0
velocity
mI = 1/2
I=½
Fig. 5 Quadrupole splitting

the electronic population of various orbitals, isomerisation phenomena, ligand structure, short-lived reaction
intermediates, semiconductor properties and the defect structure of solids.
Effect of magnetic field – magnetic splitting

When a nucleus with I > 0 is placed in a magnetic field a magnetic dipole interaction occurs between the
nuclear magnetic moment and the external magnetic field. This interaction completely removes the degeneracy of
the nuclear state and splits it into 2I+1 substates. In the case of 57Fe the ground state with I = ½ splits into two
substates and the excited state with I = 3/2 splits into four substates. The selection rule for transition is mI = 0, 1.
This leads to six possible transitions and the Mössbauer spectrum shows six absorption lines. This is shown if Fig. 6.
mI = +3/2
mI = +1/2
mI = −1/2
mI = −3/2
I = 3/2
count
velocity
mI = −1/2
I=½
mI = +1/2
Fig. 6 The effect of magnetic splitting on nuclear energy levels of 57Fe

4
Since the splitting of the spectral lines is directly proportional to the magnetic field experienced by the nucleus,
Mössbauer spectroscopy provides a very effective means by which this field may be measured. The transition
probabilities between the nuclear substates affect the intensities of the lines in the Mössbauer spectrum which can
therefore give information on the relative orientation of the magnetic field at the nucleus and the direction of
propagation of the gamma-ray beam.
The total magnetic field experienced by the nucleus is a vector sum of the field that arises due to unpaired
electrons present, if any, on the atom itself, and the field due to the external applied field. Therefore, the magnetic
field experienced depends on the oxidation state and spin state of the atom. Such field generated by the unpaired
electrons on the atom is called magnetic hyperfine field. Only unpaired electrons can contribute to it. Magnetic
hyperfine fields and its effects are observed in the Mössbauer spectra of magnetically ordered systems. When this is
changed or removed a corresponding effect will be observed in the Mössbauer spectrum.
Applications of Mössbauer spectroscopy
a. Mössbauer spectroscopy in the study of Fe (III) complexes.

3 2
The 3d5 electron configuration of iron (III) in the presence of a weak octahedral crystal field produce the 𝑡2𝑔 𝑒𝑔
6
configuration with five unpaired electrons. This gives rise to A1g ground state. Since all the d-orbitals have electrons
the charge cloud is almost spherical around the nucleus and the electric field gradient (EFG) is almost zero. Also, the
high spin iron (III), as a result of decreased shielding of s-electron wavefunctions, has a lower isomer shift than is
usually observed in iron (II) complexes. The typical value of iron (III) are 0.3 to 0.6 mms−1 depending upon the nature
of the coordination environment. As a result of these differences in isomer shift Mossbauer spectroscopy can often
be quite effective in distinguishing these different oxidation states and can therefore be helpful in studies of mixed
valence iron-containing materials.
The Mossbauer spectrum of ferrocyanide ion [Fe (CN)6]4− shows a single sharp absorption peak at a velocity of
− ½ mms−1. The [Fe(CN)6]4− ion is sufficiently symmetrical and there will not be any net electric field gradient (EFG).
But if we replace a CN group by an NO group, as in the case of the nitroprusside ion [Fe(CN) 5NO]2−, the electric field
will no longer be symmetrical and generates a net electric field gradient causing the splitting of absorption lines. This
field is not externally applied but is inherent in the structure of the ion. The Mössbauer spectra of both are given
below.
Count s−1
Count s−1
−5 0 +5 −5 0 +5
Velocity mms−1 Velocity mms−1
(a) (b)
Fig. 7, Mossbauer spectra of (a) [Fe (CN)6]4− ion and (b) [Fe(CN)5NO]2− ion
b. Mössbauer spectroscopy in the determination of Curie temperature and Néel temperature
Curie temperature (TC) is the temperature above which a ferromagnetic substance loses its ferromagnetism and
become paramagnetic. The magnetic moments in a ferromagnetic material are ordered and of the same magnitude
5
in the absence of applied magnetic field. Beyond a certain temperature the magnetic moments become disordered.
In paramagnetic material the magnetic moments are disordered in the absence of external magnetic field and
become ordered in the presence of applied field. The temperature at which magnetic disorder take place (TC) can be
conveniently determined by observing the Mössbauer spectrum of the material.

In materials that exhibit antiferromagnetism the magnetic moments of atoms or molecules align in a regular
pattern with neigbouring spins pointing in opposite directions. Like ferromagnetism this also is a demonstration of
ordered magnetism. Generally antiferromagnetic order exists at sufficiently low temperature, and the Neel
temperature (TN) is the temperature above which this magnetic ordering vanishes. The magnetic disordering can be
determined using Mössbauer spectroscopy.

The change of ordered state is often associated with small changes in the isomer shift and the quadrupole
splitting. The ordering temperatures TC or TN for the absorber can often be determined most easily by measuring the
change in counting rate with temperature at a source velocity corresponding to a maximum absorption in the
magnetic spectrum.
Compound Identification
Generally, to obtain the necessary information to understand a chemical process or identification of a new product,
the easier way is a combination of the isomer shift, the quadrupole splitting and the magnetic splitting. Frequently,
however, more information from other structural methods is needed. A few more examples are discussed here.
a. The interhalogen compound I2Br2Cl4
The compound I2Br2Cl4 was prepared by oxidizing Nal with KBrO3 followed by Cl2 gas. Its structure seems
likely to be related to that of I2Cl6, which is made from NaI and Cl2 without treatment by KBrO3. I2Cl6, is known to be a
planar molecule with a symmetrical Cl-bridged structure, Fig. 8 (a). However, there are several possible structures
for I2Br2Cl4 even within this geometric framework, such as, Fig. 8 (b), (c), (d), (e), (f), (g).
The two Br atoms could both be

bridging (8 b) or both terminal but on
different iodine atoms (8 c & d), or

both terminal but on the same iodine
atom (8 e), or one bridging and one (a)
terminal (8 f and g).
The answer to this problem

was found by Mossbauer
spectroscopy. The parameters from
(c) (d)
(b)
the l29I spectrum are given in the
following table. In the spectrum of
I2Cl6, there was one set of lines, but
in that for I2Br2Cl4 there were two
sets of lines, IA and IB. From this, we
(e) (f) (g)
can conclude that there are non-
equivalent iodine atoms. Since the Fig 8
sets were of equal intensity, it was
most unlikely that one set was due to an impurity, and so both sets were assigned to I 2Cl4Br2. This means that if the
molecule has a single structure the two iodine atoms cannot be equivalent, and so structures 8b, 8c and 8d are
already ruled out. The isomer shift  and quadrupole coupling constant EQ for one of the iodine atoms are close to
those found for I2C16 (Table below); this implies that one of the iodine atoms in I2Br2CI4 is in much the same
6
environment as are the two in I2Cl6, that is, bound to two terminal and two bridging Cl atoms. In structure 8e, one of
the iodine atoms satisfies this condition, but in structure 8f and 8g neither does, for both are bound to at least one
bromine atom. Hence the correct structure must be 8e.
Compound /mm s−1 EQ/MHz

I2Cl6 3.50  0.10 3060  10
I2Br2Cl4 IA 2.82  0.02 2916  10
IB 3.48  0.02 3040  10
b. Iron in very high oxidation states - Fe(V) and Fe(VI) nitride complexes
Until 2006, the only known Fe(VI) compounds were solid-state ferrates, which contained the FeO42− ion.
After that the first molecular Fe(VI) compounds were reported. The 57Fe isomer shifts for Fe(VI) compounds could be
expected to be extreme, because they have only two d electrons left for shielding, so the s-electron density at the
nucleus could become relatively large, and the negative nuclear factor then results in a strongly negative isomer
shift. A molecular example is the product given in Fig. 9c., which was obtained by photo-oxidation of the
azidoiron(IV) complex (Fig 9 b) at 77 K. Complex, Fig 9(b), was obtained by electro-oxidation of the azidoiron(III)
complex Fig 9 (a).
(a) (b) (c)

Fig 9: Oxidation of a series of Fe cyclam complexes.
Comparing the isomer shifts of a series of related cyclam complexes in different oxidation states, including
the two precursor compounds, shows that there is an almost linear dependence between isomer shift and oxidation
state. The photo-oxidation product gives a spectrum that can be fitted assuming that it represents two species. First,
a species with an isomer shift  = 0.53 mms−1 and a quadrupole splitting EQ = 1.13 mms−1 is present in 27%
abundance. This is assigned to a photo-reduction product of oxidation state +III. Second, the remaining 73% of the
sample is a species with an isomer shift  = − 0.29mms−1 and a quadrupole splitting EQ = 1.53 mms−1. This negative
value of  can be assigned to an oxidation state +VI in the nitride complex [(Me3-cyclam-OAc)Fe(VI)(N)]2+. It should
be noted that such values can also be computed quantum mechanically and the theoretical and experimental values
compared. This procedure can be very helpful in making assignments or verifying results for which only few data for
direct comparison exist (no other molecular Fe(VI) species in this case). The calculated isomer shift for 9(c) was −
0.31 mms−1, which agrees closely with the measured value of − 0.29mms−1. It should be noted that typical solid-state
ferrates(VI) have lower isomer shifts (about − 0.77 mms−1); this shows that the Fe=N unit, with a strong covalent
bond contribution, can be formally assigned to Fe(VI), but that its electronic structure is not like that of a typical
ferrate.
References:
1. Mössbauer spectroscopy, edtd., by Dominic P. E. Dickson and Frank J Berry
2. Fundamentals of Molecular Spectroscopy, CN Banwell and E.M. McCash
3. Molecular structure and spectroscopy, G. Aruldhas

4. Structural Methods in molecular inorganic chemistry: DWH Rankin, NW Mitzel, CA Morrison
5. Mössbauer spectroscopy – Principles and applications of the technique, Alfred G. Maddock
6. www.rsc.org, Royal Society of chemistry

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MÖSSBAUER SPECTROSCOPY

The Mössbauer Effect

embedded in a tight crystalline structure, absorption may

provides a means of using the nucleus as a probe of its environment.

57 The radioactive source nuclei are usually embedded in

well as giving the simplest possible hyperfine interaction

t1/2 =270 days

Fig. 2 spectroscopy. It represents the simplest case where the source

Isomer shift (or chemical shift)

Ground state Nucleus in sample

Fig. 5 Quadrupole splitting

Effect of magnetic field – magnetic splitting

Fig. 6 The effect of magnetic splitting on nuclear energy levels of 57Fe

changed or removed a corresponding effect will be observed in the Mössbauer spectrum.

Applications of Mössbauer spectroscopy

a. Mössbauer spectroscopy in the study of Fe (III) complexes.

conveniently determined by observing the Mössbauer spectrum of the material.

determined using Mössbauer spectroscopy.

a. The interhalogen compound I2Br2Cl4

The two Br atoms could both be

different iodine atoms (8 c & d), or

The answer to this problem

Compound /mm s−1 EQ/MHz

(a) (b) (c)

3. Molecular structure and spectroscopy, G. Aruldhas

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