Mossbauer Spectroscopy

Himalay Senapati BSc Physics, 2nd year Chennai Mathematical Institute himalay.senapati@gmail.com October 15

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Abstract Introduction

nearby atomic electrons (nuclear Zeeman splitting). 3. The shift in nuclear energy levels induced by a strong electric eld gradient due to nearby electrons (quadrupole splitting).

In 1958, Rudolf Mossbauer devised a method that allowed the phenomenon of practical resonance absorbtion and recoil-free emission of nuclear rays in solid to occur. The process is exquisitively sensitive to small dierences between the emitting and absorbing nuclei. Using this method, absorption spectroscopy became possible at a much higher resolution than was otherwise available at the time. Mossbauer spectroscopy is the science of using this phenomenon to explore the nuclear and atomic structure of materials. It is done by exploring the three phenomenas: 1. The shift in nuclear energy levels induced by the static charge of nearby atomic electrons (the isomer shift). 2. The energy level splitting in a nucleus due to the magnetic elds induced by the 1

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3.1

Theory
The Mossbauer eect

The Mossbauer Eect or recoilless nuclear resonance uorescence involves the resonant absorbtion of photons emitted by nuclei, which undergo recoilless transitions. As the line widths of these transition are very small compared to there energies, the process of resonant absorption is highly sensitive to small changes in photon energies. The resolution of Mossbauer eect is of the order of this line width per energy ie. on the order of one part in 1012 . Using Mossbauer spectrum obtained, it is possible to determine the

isomer shift, the nuclear electric quadrupole of a collection of atoms in the same state interaction, and the magnetic splitting inter- emitting photons due to transition between actions in solids. the same two energy levels for all the atoms. If this spectra is incident on a similar sample in its ground state, there is some 3.2 Recoilless emission probability that some part of the spectra will When a nucleus emits a ray, classically to get reabsorbed, raising the absorbing atoms conserve momentum it must recoil and using to excited state. This phenomena is called conservation of energy resonant absorption. E = Enucleartransition Erecoil In a transition, however, as we saw in the In a solid, due to latice interaction the eec- previous section not all of the energy goes tive mass of the nucleus increases, thus re- into the photon. Thus the distribution of ducing the recoil energy. Using quantum me- the emission and absorption energies are chanics, when the recoil energy is very less separated by two times the recoil energy. than that of emitted energy using quantiza- So the probability of resonant absorption is tion of energy the probability that the recoil proportional to the overlap of these distrienergy is zero increases, thus a large fraction butions. In the case of nuclear transition, of emissions are recoil free in a latice in suit- there is a probability of recoil free emission, able conditions. This fraction of zero phonon and likewise recoil free absorption, and thus emission, given by the Debye Waller fac- resulting in resonant absorption. On this tor, is a function of the Debye characteristic note, if recoilless emission didnt occur, ie. temperature, the ray energy and the tem- in classical picture as the line width inherent perature of the emitting and absorbing lat- by photon is vary small compared to recoil tice. The transfer of energy between nucleus energy resonant absorption shouldnt occur. and lattice is by phonon interaction at various vibrational states. As vibrational excitation is a quantized process, there is a probability that given a transition, no transfer of energy occurs between the lattice and the nucleus thus resulting in recoilless emission.

3.3

Resonant absorption

When a photon is emitted by the nucleus, given the nite lifetime of the excited state, due to energy time uncertainty principle there is an inherent uncertainty in energy. So a natural line width results in the spectra 2

3.4

els. The notable eects are Isomer shift , Quadrupole shifting and Magnetic splitWhen an emitter has a relative motion to the ting. An overview of each eect is given in absorber, the energy of the photon changes the next three sections. due to doppler shift. For non-relativistic velocities, E = h = h0 where = v/c, and 0 is the frequency of the photon emitted 3.6 Isomer Shift from an atom at rest. This is the rst-order The energy levels of a nucleus are mostly Doppler shift, valid in the limit vc. Accord- dedtermined by the strong interactions which ing to this relation, the change in photon en- binds the nucleons together. The overlap ergy is proportional to the relative velocity. of the electronic wavefunction with the nuBy varying the relative velocity of the emit- cleus will also aect the level of states, which ter, it is possible to vary photon energies over can be calculated by treating the eect as a a range of values, and thus vary the overlap- perturbation to the initial nuclear wavefuncing area in the above picture (section 3.2). tion. In dierent samples containing a given Thus by sweeping the relative velocity over a type of nucleus, but with dierent local elecrange of values and taking note of the absorp- tron wavefunction, can therefore have small tion rate, which is proportional to the over- but measurable dierent nuclear energy levlaping area, it is possible to get information els. The so called isomer shift arises due to about nuclear energy levels. In Mossbauer the non-zero volume of the and the electron spectroscopy, absorption rate is measured as charge density resulting due to s-electrons a function of source velocity. Analysis of ab- within it. This results in a monopole insorption peaks reveals information about lo- teraction, which is stated above as overlapcal state and nuclear energy levels. ing of wave function, thus altering the nu-

Doppler Shift

3.5

Observable Interactions

The energy levels of nucleus depends on a number of external factors like electric eld, magnetic eld etc. So it is possible to obtain information related to atomic and molecular structure of a sample from its mossbauer spectra as the local structure at the absorption site (absorbing nucleus) aects the nuclear energy level and thus mossbauer spectra. Depending upon the nature of internal interaction there may be a resulting split and/or shift in nuclear energy lev3

clear energy levels. Thus dierence in the local s-electron environment between the emitting nucleus and absorbing nucleus produces shift in the resonance enegy of the transition. This shifts the spectrum of absorption rate vs. relative velocity positively or negatively depending upon the s-electron density, and sets the centroid of the spectrum. If the centroid of the spectrum coincides with zero relative velocity ie. isomer shift is zero, it shows that the s-electron environment of both the absorber and the emitter are identical. As the shift can not be measured directly it is quoted relative to a known absorber. 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 ferrous ions have less s-electron at the nucleus due to the greater screening of the d-electrons. Thus ferrous ions have larger positive isomer shifts than ferric ions.

The magnitude of splitting, is related to the nuclear quadrupole moment, Q and the principle component of the EFG, Vzz by the relation = eQVzz . 2

3.7

Electric Quadrapole Splitting 3.8

Magnetic Splitting

Nuclei in states with an angular momentum quantum number l 1/2 have a non-spherical charge distribution. This distribution is expanded as a multipole, and approximated up to quadrupole moment. In the presence of an asymmetrical electric eld produced by an asymmetric electronic charge distribution or ligand arrangement this quadrupole moment splits the nuclear energy levels. The charge distribution is charecterised by a single quantity called the Electric Field Gradient (EFG). In the case of an isotope with a l = 3/2 excited state, the excited state is split into two substates ml = 1/2 and ml = 3/2. This is shown in the following gure, giving a two line spectrum or doublet. 4

In the presence of a magnetic eld B the nuclear spin moment experiences a dipolar interaction with the magnetic eld. The energy associated with the interaction is given by EM = .B . There are many sources of magnetic elds that can be experienced by the nucleus.The total eective magnetic eld at the nucleus, Be f f is given by Bef f = (Bcontact )+Borbital +Bdipolar )+Bapplied , the rst three terms being due to the atoms own partially lled electtron shells. Bc ontact is due to the spin on those electrons polarising the spin density at the nucleus, Borbital is due to the orbital moment on those electrons, and Bdipolar is the dipolar eld due to the spin of those electrons. This magnetic eld splits the nuclear energy level with a spin of l into (2*l+1) substates.

Data Analysis

The Data analysis has been done by taking the digital output from the mossbauer spectroscope and using Gnu Plot to calculate Isomer Shift, Magnetic Splitting and Quadrupole Splitting. Origin has been used to analyse the peaks. The peaks have been approximated with a Gaussian Prole. There are two data sets, one corresponding to quadrupole splitting, and other to magnetic splitting of 57 F e. In the above image transition between excited and ground state of 57 F e has been shown, keeping selection rules in mind which states for the transition to be possible only when ml is 0 or 1. This gives six possible trasnsition between 3/2 to 1/2 with the line spacing being proportional to Bef f . The line positions are related to the splitting of the energy levels, but the line intensities are related to the angle between the Mossbauer gamma-ray and the nuclear spin moment.The plot is symmetric about the centroid of the spectrum. The outer, middle and inner line intensities are related by 3 : 4sin2 : 1. In polycrystalline samples with 1+cos2 no applied eld the middle term averages to 2 but in single crystals or under applied elds the relative line intensities can give information about moment orientation and magnetic ordering. To simplify things, source is prepared such that the gamma rays themselves dont split into dierent energy levels.

The above plot is the mossbauer spectum of 57 F e. The centroid of the spectrum is derived by taking the average of the two peaks. The peak position is given by .48 and -1.26. Isomer shift is given by -.39 which indicates a negative shift, and thus implying higher oxidation number of the absorber than the emitter. The number of transition shows that there is no magnetic splitting. The dierence between the two peaks = 1.74 as stated before is proportional to the nuclear quadratic 5

dipole moment. It can be found out by calibrating the instrument with a known sample.

The centroid of the spectrum derived by taking the average of the peak positions and noting that peaks of equal intensity are symmetric with respect to it. The centroid comes out to be at x = -.11. The number of transition conrms magnetic splitting. The Isomer shift = -.11 implies higher oxidation number of the absorber than the emitter.