Mossbauer spectroscopy factor

The recollless fraction, that Is, the relative number of events In which no exchange of momentum occurs between the nucleus and Its environment. Is determined primarily by the quantum mechanical and physical structure of the surrounding media. It Is thus not possible to observe a Mossbauer effect of an active nucleus In a liquid, such as an Ion or a molecule In solution. This represents a serious limitation to the study of certain phenomena It allows, however, the Investigation of films or adsorbed molecules on solid surfaces without Interference from other species In solution. This factor In conjunction with the low attenuation of Y-rays by thin layers of liquids, metals or other materials makes Mossbauer spectroscopy particularly attractive for situ studies of a variety of electrochemical systems. These advantages, however, have not apparently been fully realized, as evidenced by the relatively small number of reports In the literature (17). 

In order to understand the Mossbauer effect and the importance of recoUless emission and absorption, one has to consider a few factors that are mainly related to the fact that the quantum energy of the y-radiation used for Mossbauer spectroscopy (Eo K, 10-100 keV) is much higher than the typical energies encountered, for instance, in optical spectroscopy (1-10 eV). Although the absolute widths of the... 

An important accessory in many applications of Mossbauer spectroscopy is a cryostat for low temperature and temperature-dependent measurements. This may be necessary to keep samples frozen or to overcome small Debye-Waller factors of the absorbers at room temperature in the case of an isotope with high y-energy. Paramagnetic samples are measured at liquid-helium temperatures to slow down... 

For a comparison of experimental Mossbauer isomer shifts, the values have to be referenced to a common standard. According to (4.23), the results of a measurement depend on the type of source material, for example, Co diffused into rhodium, palladium, platinum, or other metals. For Fe Mossbauer spectroscopy, the spectrometer is usually calibrated by using the known absorption spectrum of metallic iron (a-phase). Therefore, Fe isomer shifts are commonly reported relative to the centroid of the magnetically split spectrum of a-iron (Sect. 3.1.3). Conversion factors for sodium nitroprusside dihydrate, Na2[Fe(CN)5N0]-2H20, or sodium ferrocyanide, Na4[Fe(CN)]6, which have also been used as reference materials, are found in Table 3.1. Reference materials for other isotopes are given in Table 1.3 of [18] in Chap. 1. 

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. 

Mossbauer spectroscopy with started only in 1965, when Harris et al. [322] measured the Mossbauer absorption spectra of the 99 keV transition of Pt in platinum metal as a function of temperature (between 20 and 100 K) and of absorber thickness and derived the temperature dependence of the Debye-Waller factor. 

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 great advantage of Mossbauer spectroscopy for catalyst research is that it uses 7-radiation of high penetrating power such that the technique can be applied in situ. An economic advantage is that the technique is relatively inexpensive. The price is about a factor of ten less than equipment for electron microscopy or photoelectron spectroscopy. 

The rapid progress in the understanding of the active site of aconitase in the 1980 s has primarily originated from the work of H. Beinert and his collaborators. Three essential factors contributed to the success of this work 1) a ready and consistent source of enzyme (gram quantities), 2) a solid chemical and biochemical understanding of aconitase, and 3) close interactions with outstanding collaborators (most notably E. Munck s group for Mossbauer spectroscopy and B. M. 

An iron-promoted cobalt molybdate catalyst (Fe0 03Co0.9 7MoO4) was studied by Maksimov et al. [195,196] with respect to the role of iron in the transfer of charge. Iron strongly enhances the catalytic activity and at the same time increases the conductivity by a factor of 100. Mossbauer spectroscopy reveals that 4% of the iron ions are present as Fe2+ impurity . This fraction is doubled at steady state reaction conditions, and indicates participation of iron in the charge transfer process. 

The exponential term is a Thomas-Fermi screening factor which accounts for the screening by the core electrons. Direct measurement of the ionic character of a bond is a complex operation. In principle, a number of techniques such as X-ray or neutron diffraction, nmr, photoelectron or Mossbauer spectroscopy provide information about electron distribution and charge density in practice the results are usually far from unambiguous. 

Independent of whether or not a well-defined crossover temperature can be observed in NS data above Tg, it has been well known for a considerable time that on heating a glass from low temperatures a strong decrease of the Debye-Waller factor, respectively Mossbauer-Lamb factor, is observed close to Tg [360,361], and more recent studies have confirmed this observation [147,148,233]. Thus, in addition to contributions from harmonic dynamics, an anomalously strong delocalization of the molecules sets in around Tg due to some very fast precursor of the a-process and increases the mean square displacement. Regarding the free volume as probed by positron annihilation lifetime spectroscopy (PALS), for example, qualitatively similar results were reported [362-364]. 

This technique, besides allowing determination of the Lamb-Mossbauer factor, provides direct access to the density of phonon states for the probe isotope in a solid. It thus provides information about lattice dynamics that is excluded by the limitations of Mossbauer spectroscopy. This technique could be valuable in investigations of adsorption with the adsorbing element as the probe and showing the modifications brought about by the adsorbate on the dynamic properties of the probe. 

For liquid solutions containing iron compounds or proteins, the Mossbauer-Lamb factor goes to zero, and therefore Fe Mossbauer spectroscopy on solutions is only possible in the frozen state. Since the natural abundance of Fe is only 2%, it is advisable to perform Mossbauer studies on solutions with Fe-enriched samples. For protein studies, Fe enrichment is essential. Typical sample volumes can range from 0.25-1.0mL. In some cases, frozen solution studies can be performed down to an Fe concentration of 0.1 mM, but taking a Mossbauer spectrum of such a sample can take weeks depending on the shape of the spectrum and the outcome is uncertain. Therefore, it is strongly recommended that the concentration of Fe be at least 1 mM. Samples with Fe concentrations of, for example, 10 mM can very conveniently be measured in a couple of hours—such samples the Mossbauer spectroscopists like the most. In any case, for... 

The AAS method has several limitations. For the trace elements, particularly the colorants cobalt and nickel, the dilution factor required for analyses of 12 elements by continuous nebulization places these elements close to the detection limits for flame AAS. More accurate data on these and other trace elements are necessary before conclusions can be drawn on the source minerals used to impart color. Phosphorus, a ubiquitous minor component of medieval stained glass, has not been determined by AAS in the course of this work, but has the potential to provide key information on sources of plant ash. A full understanding of the colorant role of the transition metal elements is not possible on the basis of analysis alone UV-visible spectroscopy, electron spin resonance spectrometry, and Mossbauer spectroscopy, for example, are necessary adjuncts to achieve this aim. The results of the application of these techniques and the extension of the AAS method to trace element determination by pulse nebulization and furnace atomization will be addressed in future reports. 

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