Mossbauer resonant fraction

At 5 K, the spectrum is dominated (area fraction of 80%) by a singlet, typical for one of the rare cases of cubic local symmetry for low-spin Fe(II). In addition, two distinct high-spin Fe(II) doublets are observed, contributing 16 and 4%, respectively. The presence of two high-spin Fe(II) doublets together with the fact that the Mossbauer resonance lines arising from the... 

Mossbauer spectroscopy involves the measurement of minute frequency shifts in the resonant gamma-ray absorption cross-section of a target nucleus (most commonly Fe occasionally Sn, Au, and a few others) embedded in a solid material. Because Mossbauer spectroscopy directly probes the chemical properties of the target nucleus, it is ideally suited to studies of complex materials and Fe-poor solid solutions. Mossbauer studies are commonly used to infer properties like oxidation states and coordination number at the site occupied by the target atom (Flawthome 1988). Mossbauer-based fractionation models are based on an extension of Equations (4) and (5) (Bigeleisen and Mayer 1947), which relate a to either sums of squares of vibrational frequencies or a sum of force constants. In the Polyakov (1997)... 

One also sees that at room temperature the two peaks of the quadru-pole split pattern are different in intensity. This difference disappears at 77°K. It is an example of what is known as the Gordanskii effect 10) and is caused by the fact that the amplitude of vibration is different, parallel to the surface and normal to the surface, so that the effective resonant fraction is different for the two halves of the quadrupole splitting. This effect has been extensively studied by the Russians. In a recent paper, Suzdalev and others report a study of tin in the surface of silica gel 18), They put calcium ions in the surface of silica gel, then replaced them with divalent tin by ion exchange. The result was a mixture of stannous and stannic ions, and of course, the use of the Mossbauer effect made it possible to determine accurately the relative amounts of the two. They studied the amplitude of vibration of the two kinds of atoms and found, for example, for the stannous ions, the r.m.s. amplitude of vibration parallel to the surface was 0.07 A., and the r.m.s. amplitude of vibration perpendicular to the surface was about twice as great—about 0.13 A. Karasev and others have also worked on the chemistry of adsorbed... 

Wender and Hershkowitz [237] used the sensitivity of the recoil-free fraction in tungsten Mossbauer spectroscopy to deduce the effect of irradiation of tungsten compounds by Coulomb excitation of the resonance levels (2 states of I82,i84,i8 y with 6 MeV a-particles. While no effect of irradiation on the/-factors could be observed for tungsten metal in agreement with [233], a decrease of/was measured for WC, W2B, W2B5, and WO3 after irradiation. 

The Mossbauer effect involves the resonance fluorescence of nuclear gamma radiation and can be observed during recoilless emission and absorption of radiation in solids. It can be exploited as a spectroscopic method by observing chemically dependent hyperfine interactions. The recent determination of the nuclear radius term in the isomer shift equation for shows that the isomer shift becomes more positive with increasing s electron density at the nucleus. Detailed studies of the temperature dependence of the recoil-free fraction in and labeled Sn/ show that the characteristic Mossbauer temperatures Om, are different for the two atoms. These results are typical of the kind of chemical information which can be obtained from Mossbauer spectra. 

A possible modification of this expression is presented elsewhere (82). The value of t, can be related to a diffusion coefficient (e.g., tj = l2/6D, where / is the jump distance), thereby making the Ar expressions qualitatively similar for continuous and jump diffusion. A point of major contrast, however, is the inclusion of anisotropic effects in the jump diffusion model (85). That is, jumps perpendicular to the y-ray direction do not broaden the y-ray resonance. This diffusive anisotropy will be reflected in the Mossbauer effect in a manner analogous to that for the anisotropic recoil-free fraction, i.e., for single-crystal systems and for randomly oriented samples through the angular dependence of the nuclear transition probabilities (78). In this case, the various components of the Mossbauer spectrum are broadened to different extents, while for an anisotropic recoil-free fraction the relative intensities of these peaks were affected. 

Consider first a Mossbauer isotope with a large associated resonant irradiation energy. The large recoil energy thus results in a small recoil-free fraction, and in the transmission mode the Mossbauer effect is only observed by measuring a small change in the primary beam intensity. The radiation reemitted as a result of these recoil-free events may, however, be superimposed on a weak background if observed for a direction different from the primary beam (SO). Thus, measurement of this radiation intensity versus... 

In a basic Mossbauer experiment, the reduction in transmission (9) (Figure 2) or the increase in scattered intensity of radiation (2) (Figure 3) is observed as a function of the relative velocity between a source and an absorber. The full width at half maximum of the resonance curve r is related to the mean life of the radiating state by the uncertainty relation r 2h/r. The depth of the curve, c, is related to /, the magnitude of the recoilless fraction of gamma rays emitted, and hence to the crystalline properties of the solid. Finally, the displacement of the curve from zero relative velocity indicates the energy difference between emitted and absorbed radiation and is proportional to the s-electron... 

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