Mossbauer temperature

Fig. 4.2 Temperature dependence of the isomer shift due to the second-order Doppler shift, sod- The curves are calculated for different Mossbauer temperatures 0m by using the Debye model whereby the isomer shift was set to (5 = 0.4 mm s and the effective mass to Meff =100 Da, except for the dashed curve with Meff = 57 Da...

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. 

Mossbauer spectroscopy can only be used to obtain rates of interconversion if the lifetimes are close to 10 7 second. As described in Section III,E a few examples satisfying this condition have been found. Some questions remain over the quantitative interpretation of the data. Nevertheless, spin-equilibrium relaxation lifetimes have been estimated from Mossbauer temperature-dependent linewidths for two salts of an iron(III) complex, [Fe(acpa)2]+. The lifetimes are of the order 10 5—10 7 second over temperature ranges from 100 to 300 K (109, 111). 

Mossbauer and Wiedemann 1960) where is the recoil energy (= 3.13425 x 10 J for the 14.4 keV transition of Fe), ke is the Boltzmann constant, and 0m is the characteristic Mossbauer temperature, where m can be determined from temperature dependant measurements of the centre shift as described by Equation (2). The recoil-free fraction of the absorber can also be determined through temperature dependant measurements of the relative area according to Equation (13). In either case, a phase transformation can be recognised as either a discontinuity or a change in slope of the recoil-free fraction plotted as a function of temperature. 

Doublet 1 may be assigned unambiguous to P4 symmetry, since the hyperfme parameters follow the expected behaviour for Fe in a relatively undistorted tetrahedral site. The high value of quadrupole splitting indicates a high valence contribution, and displays the expected temperature variation for tetrahedral environments bb 1968). The characteristic Mossbauer temperature 0m is in the range expected for Fe (De Grave and Van Alboom 1991). 

The same magnetic dependence on temperature was also demonstrated for unsolvated Fe[papt] (694). and a detailed Mossbauer study established that the spin transition is thermally... 

As shown in Fig. 7.6, the Mossbauer data show a reduction in Morin transition temperature with increasing shock severity. At temperatures below the transition, increasing shock severity causes greater retention of the higher temperature, weak ferromagnetic contribution. The measure of weak ferromagnetic (WF) fraction (the high temperature form) is a sensitive indication of shock modification. 

Four different material probes were used to characterize the shock-treated and shock-synthesized products. Of these, magnetization provided the most sensitive measure of yield, while x-ray diffraction provided the most explicit structural data. Mossbauer spectroscopy provided direct critical atomic level data, whereas transmission electron microscopy provided key information on shock-modified, but unreacted reactant mixtures. The results of determinations of product yield and identification of product are summarized in Fig. 8.2. What is shown in the figure is the location of pressure, mean-bulk temperature locations at which synthesis experiments were carried out. Beside each point are the measures of product yield as determined from the three probes. The yields vary from 1% to 75 % depending on the shock conditions. From a structural point of view a surprising result is that the product composition is apparently not changed with various shock conditions. The same product is apparently obtained under all conditions only the yield is changed. 

Figure 2. Room temperature Mossbauer spectra of amorphous Fe2oNi8o sample, a) before heating b) after heating at 483 K for 10 h c) after heating at 693 K for 5 h...

Electrobalances suitable for thermogravimetry are readily adapted for measurements of magnetic susceptibility [333—336] by the Faraday method, with or without variable temperature [337] and data processing facilities [338]. This approach has been particularly valuable in determinations of the changes in oxidation states which occur during the decompositions of iron, cobalt and chromium oxides and hydroxides [339] and during the formation of ferrites [340]. The method requires higher concentrations of ions than those needed in Mossbauer spectroscopy, but the apparatus, techniques and interpretation of observations are often simpler. 

Product yields may also be determined by magnetic measurements, as in the formation of ferrites [340], where kinetic data were obtained at reaction temperature. Quantitative applications of Mossbauer spectroscopy have also been described [326]. 

For example, octahedral quadrupole splitting observed for the cis-octahedral analogs 7,8). More recently, temperature-dependent Mossbauer measurements have been used in conjunction with Raman spectroscopy to determine molecular weights 453) and lattice rigidity 460) of various organotin compounds. 

Another point of contention has been the extent to which, if any, SbFj is reduced to SbFs upon intercalation. Although chemical analyses have shown an F Sb ratio of 5 1 (Lll, M5), Sb Mossbauer measurements (B24) indicated partial reduction of Sb(V) to Sb(III). On the other hand, mass-spectral measurements as a function of temperature (S15) showed only SbFs, evolved in stages, with no fluorocarbons emitted at any time. The latter are usually an indication of partial reduction of the intercalant and fluorination of the graphite host. Wide-line, F-NMR chemical-shifts are consistent with either SbFj or SbFe, but not with SbFs, but the occurrence of fluorine exchange could produce minor amounts of trivalent species (FI 1) this point is thus still controversial, and will be alluded to again. 

A major discrepancy that remains unresolved in the excited-state properties of the [Fe384]° cluster in D. gigas Fdll concerns the existence of a low-lying, fully valence-delocalized state that becomes populated at temperatures above 25 K. 8uch a state is clearly apparent in the temperature-dependent Mossbauer studies of reduced D. gigas Fdll (29) and P. furiosus 3Fe Fd (198) and is represented by one quad-rupole doublet with AEq 0.9 mm/s and S = 0.45 mm/s. 8uch a... 

An important advance on these studies was the possibility of isolating AORs from Fe enriched media with obvious interest for an iron-sulfur center site labeling, with enhanced sensitivity of the Mossbauer studies. The work developed with bacterial systems is advantageous as compared with mammalian systems for isotopic labeling and opens the possibility of a direct measurement of substrate binding. Spectra of the enzyme in oxidized, partially reduced, benzaldehyde-reacted, and fully reduced states were recorded at different temperatures and with variable externally applied magnetic fields (222). In the oxidized enzyme, the clusters are diamag-... 

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