Mossbauer spectroscopy basics

This review will introduce basic techniques for calculating equilibrium and kinetic stable isotope fractionations in molecules, aqueous complexes, and solid phases, with a particular focus on the thermodynamic approach that has been most commonly applied to studies of equilibrium fractionations of well-studied elements (H, C, N, O, and S) (Urey 1947). Less direct methods for calculating equilibrium fractionations will be discussed briefly, including techniques based on Mossbauer spectroscopy (Polyakov 1997 Polyakov and Mineev 2000). 

In the following section, we describe the case of adsorption of a Sn complex onto a palladium oxide suspension. In an alkaline medium (a basic PdO hydrosol), chlorides in the SnCL complex are substituted in the coordination sphere of tin(IV) by hydroxo anions, which are in excess, yielding the stannate Sn(OH)g complex. The Sn Mossbauer spectroscopy spectrum of a bimetallic sol (frozen in liquid nitrogen) is compared with a true stannic solution. At the same tin concentration, it shows the changes in the Sn environment due to adsorption onto the PdO surface (Fig. 13.27). The isomer shift S is found to be close to zero for the stannate solution and increases when contacted with the PdO suspension, indicating a modification of the coordination sphere of tin. The increase in 5 can be correlated to an increase in the core level electronic density of tin. The quadrupole splitting A, is related to a modification of the symmetry of the close environment of tin, due to adsorption of Sn(OH)g complexes onto the PdO colloidal nanoparticles. 

Despite all the information that might be obtained using Mossbauer spectroscopy, some of its limitations naturally discouraged many chemists from using this new technique. Unfamiliarity with the basic principles, the fact that most of the early work was done only on iron and tin, and the lack of commercially available research quality equipment until 1965 were other reasons for the lack of interest. This symposium. The Mossbauer Effect and Its Application in Chemistry, was sponsored by Nuclear Science (formerly Nuclear Science Engineering Corp.), a division of International Chemical Nuclear Corp., with the hope that more chemists would learn how Mossbauer spectroscopy has been and can be used. 

In a recent study, Fernandez-Bertran et al. used mechanochemical reactions to prepare a number of hemin complexes with amino acids such as arginine, histidine, lysine, methionine and tryptophan. The basic amino acids react with the hemin peripheral propionic acid groups, while arginine is also able to form a pentacoordinated complex at the Fe(III) centre. The reactions were followed by IR and Mossbauer spectroscopies [77a]. The solid-state reaction of hemin with KCN, Na2S and various substituted imidazoles has also been investigated [77b]. 

Other Papers.—Various iron species prepared by the vacuum pyrrolysis of acetyl-ferrocene-furfural resins at 400°C have been studied by Mossbauer spectroscopy. These consist of an amorphous glass-like carbon matrix containing free iron atoms, Fe+ ions, iron clusters, superparamagnetic iron, and ferromagnetic iron.333 The effect of pressure of up to 50kbar on the absorption spectra of five iron(m), two iron(n) and one mixed valence compound has been studied. In six of the compounds, but not in basic ferric acetate or soluble Prussian Blue, the observed pressure-induced bands were assigned to d-d transitions of converted iron(n) for the ferric compounds and to spin-forbidden d-d bands for the ferrous compounds. The charge-transfer band from iron(n) to iron(m) in soluble Prussian Blue showed a blue shift at pressures up to 7.2 kbar.334... 

Mossbauer spectroscopy may be important and useful when applied to electrodes which contain ferromagnetic components. It is basically an in situ tool which provides valuable information on possible orientation and oxidation states of ferromagnetic species in the electrodes as a function of the electrochemical process and the potential applied. For example, electrodes for oxygen reduction may be highly catalytic when containing macrocycles with transition metal cations such as Fez+, Niz+, Coz+ [89,90], A typical apparatus for this technique is described in Ref. 91. 

The transitions involved in the Mossbauer effect and the basic principle of Mossbauer spectroscopy, occur where the area is enclosed by a dash box and kept at cryogenic temperature. 

For basic details of ESR (also referred to as EPR) spectroscopy, see R.V. Parish (1990) NMR, NQR, EPR and Mossbauer Spectroscopy in Inorganic Chemistry, Ellis Horwood, Chichester. 

Mossbauer spectroscopy makes it possible to obtain experimental information which is basically of local character. From fitting of the spectra observed one may... 

The rigidity of the basic silicate structures exerts a greater controlled influence on cation site symmetries than do the individual cation charges, an important difference from the oxides where the anions have more freedom of movement. The ease with which Fe and Fe + cations can be distinguished and site occupancies determined in oxides by Mossbauer spectroscopy suggests a logical extension to similar studies in silicates, and considerable progress has been made in this direction. 

Mossbauer spectroscopy and NMR spectroscopy have in common that they provide information which is basically local in character. Up to now the Mossbauer effect has been more fruitfully applied to amorphous alloys than NMR. There are several reasons for this. In ferromagnetic materials the NMR can give rise to much more accurate values of the hyperfine fields than the Mossbauer effect. Owing to the extremely large line broadening this advantage is lost in amorphous alloys. 

Abstract. Undoubtedly there is special interest focused on the capability of Mossbauer effect spectroscopy as a useful technique for the elucidation of scientific problems in structural chemistry and bonding phenomena in inorganic materials. In the present discussion an attempt has been made to summarize some of the basic and important aspects in interpretation of spectral analysis by means of application on a routine base, of Mossbauer spectroscopy in materials science. A number of applications extracted mainly from data in the literature have been used for different kind of inorganic materials (including glasses and ceramic materials) to illustrate the kind of information one may obtain from the Mossbauer spectra with Fe, Sn, Te and Sb types of Mossbauer isotopes. 

Soluble pigments The most important pigments in this class are the metallic chromates, which range in solubilities from 17 0 to O-OOOOSg/1 CrOf . An examination has recently been carried out of the mechanism of inhibition by chromate ions and it has been shown by chemical analysis of the stripped him, Mossbauer spectroscopy and electron microprobe analysis that the air-formed film is reinforced with a more protective material in the form of a chromium-containing spinel (Chapter 17). The situation is, however, complicated by the possibility that some chromates, particularly the basic ones, may inhibit through the formation of soaps. There is evidence that lead chromate can function in this way. 

Mossbauer spectroscopy with synchrotron radiation can be used in a straightforward manner with single-line Fe Mossbauer sources obtained using iron borate (FeBOs) single crystals set under diffraction conditions at the Neel temperature (75.3°C) (Smirnov et al. 1969, 1997 Smirnov 1999 Mitsui et al. 2005, 2007). In this method, the spectrum obtained using synchrotron Mossbauer sources is basically identical to that obtained using conventional radioactive sources. This approach, therefore, is easily applicable and beneficial for a wide range of Mossbauer research. However, Fe is the only available nuclide so far. 

Mossbauer spectroscopy is a versatile technique that is useful in many areas of science such as Physics, Chemistry, Biology, and Metallurgy. It yields very precise information about the chemical, structural, magnetic properties of a material. The basic feature of the technique is the discovery of recoUless y-ray emission and absorption, now referred to as the Mossbauer Effect, after its discoverer Rudolph Mossbauer, who reported the effect in 1958 (Mossbauer 1958) and was awarded the Nobel Prize in 1961 for his pioneer work. 

The aim of this chapter is to report on recent advances in the in situ Mossbauer spectroscopy with synchrotron radiation on thin films that became possible due to the instrumentation developments at the nuclear resonance beamline ID 18 of the ESRF. After a detailed description of the beamline and of the UHV system for in situ experiments, a brief introduction into the basic NRS techniques is given. Finally, the application of these techniques to investigate magnetic, diffusion, and lattice dynamics phenomena in ultrathin epitaxial Fe films deposited on a W(l 10) substrate is presented and discussed. 

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