Recoil energy, Mossbauer studies

The recoilless nuclear resonance absorption of y-radiation (Mossbauer effect) has been verified for more than 40 elements, but only some 15 of them are suitable for practical applications [33, 34]. The limiting factors are the lifetime and the energy of the nuclear excited state involved in the Mossbauer transition. The lifetime determines the spectral line width, which should not exceed the hyperfine interaction energies to be observed. The transition energy of the y-quanta determines the recoil energy and thus the resonance effect [34]. 57Fe is by far the most suited and thus the most widely studied Mossbauer-active nuclide, and 57Fe Mossbauer spectroscopy has become a standard technique for the characterisation of SCO compounds of iron. 

The Mossbauer effect is the emission and resonant absorption of nuclear y-rays studied under conditions such that the nuclei have negligible recoil velocities when y-rays are emitted or absorbed. This is only achieved by working with solid samples in which the nuclei are held rigidly in a crystal lattice. The energy, and thus the frequency of the y-radiation involved, corresponds to the transition between the ground state and the short-lived excited state of the nuclide concerned. Table 2.4 lists properties of several nuclei which can be observed using Mdssbauer spectroscopy. 

Equation (1.10) indicates that the probability of zero-phonon emission decreases exponentially with the square of the y-ray energy. This places an upper limit on the usable values of Ey, and the highest transition energy for which a measurable Mdssbauer effect has been reported is 155 keV for Os. Equation 1.10 also shows that/increases exponentially with decrease in which in turn depends on the firmness of binding and on the temperature. The displacement of the nucleus must be small compared to the wavelength X of the y-ray. This is why the Mossbauer effect is not detectable in gases and non-viscous liquids. Clearly, however, a study of the temperature dependence of the recoil-free fraction affords a valuable means of studying the lattice dynamics of crystals. 

When a nucleus emits or absorbs a y-photon without loss of energy from recoil of the nucleus or from thermal broadening effects, the phenomenon is referred to as the Mossbauer effect. The y-photon is monochromatic to 1 part in 10 °-10 and this extremely well-defined electromagnetic radiation can be used to study the very small differences in the energy of interaction between a nucleus and its extra-nuclear electrons when a Mossbauer atom is sited in different chemical and physical environments. 

Mossbauer spectroscopy is specialized, but it can be invaluable when it is available. The technique relies on the recoil-free emission and resonant absorption of y-rays by nuclei that are bound in the solid state. (If it is not in a solid, the free nucleus recoils and no resonance is detected.) To see this resonance, we have to match the energy of the y-ray emitter to the energy of the absorber (the sample), which means that only a small number of elements can be studied. Two that can be studied are tin and iron. The technique gives information on the bonding and coordination, and on the valence (oxidation) state. Since the technique relies on Z, it works for particular isotopes, Fe for iron with Co as the radioactive source of y-rays. (Natural Fe contains -2.19 wt% Fe.)... 

Unfortunately, the requirements of recoil-free emission and resonant absorption and transmission through the absorber limit the useable energy range of the Mossbauer effect 7-ray to approximately 10-100 keV. Further, in order to obtain rather sharp absorption lines and a reasonable spectral resolution, the mean lifetime of the Mossbauer 7-ray precursor state should be between 1 ns and 100 ns. Further, the Mossbauer nuclide must have a sufficiently high isotopic abundance in the element to yield a usable signal-to-noise ratio over a reasonable acquisition time. Finally, the radioactive source containing the Mossbauer 7-ray precursor state must be easily prepared and have a mean lifetime of several weeks to be practical. These various requirements limit the number of nuclides available for typical Mossbauer spectral studies. 

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