Mossbauer spectroscopy transition

The Mossbauer nucleus can, therefore, be used as an observer or probe to obtain information about site symmetries and field gradients, much as in NQR spectroscopy. However, whereas in NQR transitions are observed directly between ground-state sublevels, in Mossbauer spectroscopy transitions between sublevels of the excited state and the ground-... 

Mossbauer spectroscopy of AvF clearly demonstrated the presence of P clusters (174). The EPR spectra of dithionite-reduced VFe proteins are complex, indicating the presence of several paramagnetic species. Avl exhibits broad EPR signals, with g values of 5.8 and 5.4 integrating to 0.9 spins per V atom, which have been assigned to transitions from the ground and first excited state of a spin S = system (175). EPR data for AcF are more complex, with g values at 5.6, 4.3, and 3.77 that appear to arise from a mixture of S = species (176). The signals were associated with a midpoint potential of... 

Of special Interest as O2 reduction electrocatalysts are the transition metal macrocycles In the form of layers adsorptlvely attached, chemically bonded or simply physically deposited on an electrode substrate Some of these complexes catalyze the 4-electron reduction of O2 to H2O or 0H while others catalyze principally the 2-electron reduction to the peroxide and/or the peroxide elimination reactions. Various situ spectroscopic techniques have been used to examine the state of these transition metal macrocycle layers on carbon, graphite and metal substrates under various electrochemical conditions. These techniques have Included (a) visible reflectance spectroscopy (b) laser Raman spectroscopy, utilizing surface enhanced Raman scattering and resonant Raman and (c) Mossbauer spectroscopy. This paper will focus on principally the cobalt and Iron phthalocyanlnes and porphyrins. 

P. Giitlich et al., Mossbauer Spectroscopy and Transition Metal Chemistry,... 

Up to the present time, the Mossbauer effect has been observed with nearly 100 nuclear transitions in about 80 nuclides distributed over 43 elements (cf. Fig. 1.1). Of course, as with many other spectroscopic methods, not all of these transitions are suitable for actual studies, for reasons which we shall discuss later. Nearly 20 elements have proved to be suitable for practical applications. It is the purpose of the present book to deal only with Mossbauer active transition elements (Fe, Ni, Zn, Tc, Ru, Hf, Ta, W, (Re), Os, Ir, Pt, Au, Hg). A great deal of space will be devoted to the spectroscopy of Fe, which is by far the most extensively used Mossbauer nuclide of all. We will not discuss the many thousands of reports on Fe... 

Giitlich, P., Link, R., Trautwein, A.X. Mossbauer Spectroscopy and Transition Metal Chemistry. Inorganic Chemistry Concepts Series, vol. 3, 1st edn. Springer, Berlin (1978)... 

The ratio F/Eq of width F and the mean energy of the transition Eo defines the precision necessary in nuclear y-absorption for tuning emission and absorption into resonance. Lifetimes of excited nuclear states suitable for Mossbauer spectroscopy range from 10 s to s. Lifetimes longer than 10 s produce too... 

The previous chapters are exclusively devoted to the measurements and interpretation of Fe spectra of various iron-containing systems. Iron is, by far, the most extensively explored element in the field of chemistry compared with all other Mdssbauer-active elements because the Mossbauer effect of Fe is very easy to observe and the spectra are, in general, well resolved and they reflect important information about bonding and structural properties. Besides iron, there are a good number of other transition metals suitable for Mossbauer spectroscopy which is, however, less extensively studied because of technical and/or spectral resolution problems. In recent years, many of these difficulties have been overcome, and we shall see in the following sections a good deal of successful Mossbauer spectroscopy that has been performed on compounds of... 

In Table 7.1 at the end of the book), nuclear data are collected for those Mdssbauer transitions of transition metal nuclides that are used in Mossbauer spectroscopy. The symbols used in this table have the following meaning ... 

MS2 NiSAl-91 < X < 2.1) Nii j,CUySi.93 (0.03 < y < 0.1) Investigation of structural, electronic, and magnetic properties by means of X-ray diffraction, densitometry, resistivity, susceptibility, and Ni Mossbauer spectroscopy as function of x temperature of phase transition from semimetalhc to metallic state as function of x different Ni sites with different (l/f l) and different angle between H and EFG axis effect of Cu impurities... 

The isotope is almost exclusively used for the investigation of chemical compounds. The resolving power of Mossbauer spectroscopy is demonstrated by the spectra from WS2 powder and single-crystal measurements as shown in Fig. 7.48 (from [222]). On the right-hand side of the picture, the angular dependence of E2 transitions for Aw = 2, 1,0 hyperfine components is indicated. 

The application of Mossbauer spectroscopy in chemistry requires a prior knowledge of the nuclear states and transitions involved. In this section, we shall describe the determination of nuclear parameters by means of Mossbauer experiments with Os nuclei. 

There are two iridium isotopes, ir and Ir, suitable for Mossbauer spectroscopy. Each of them possesses two nuclear transitions with which nuclear resonance absorption has been observed. Figure 7.58 (from [266]) shows the (simplified) nuclear decay schemes for both iridium Mossbauer isotopes the Mossbauer transitions are marked therein with bold arrows. The relevant nuclear data known to date for the four Mossbauer transitions are collected in Table 7.1 at the end of the book. 

It is a matter of historical interest that Mossbauer spectroscopy has its deepest root in the 129.4 keV transition line of lr, for which R.L. Mossbauer established recoilless nuclear resonance absorption for the first time while he was working on his thesis under Prof. Maier-Leibnitz at Heidelberg [267]. But this nuclear transition is, by far, not the easiest one among the four iridium Mossbauer transitions to use for solid-state applications the 129 keV excited state is rather short-lived (fi/2 = 90 ps) and consequently the line width is very broad. The 73 keV transition line of lr with the lowest transition energy and the narrowest natural line width (0.60 mm s ) fulfills best the practical requirements and therefore is, of all four iridium transitions, most often (in about 90% of all reports published on Ir Mossbauer spectroscopy) used in studying electronic stractures, bond properties, and magnetism. 

The early Mossbauer studies using (mostly) the Ir (73 keV) transition up to about 1983 has been reviewed in an article by Wagner [298]. The author discusses all aspects of practical Mossbauer spectroscopy with this iridium probe, such as... 

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. 

Shinjo et al. have investigated a number of multilayers and interfaces, also by Sn Mossbauer spectroscopy [437 39], as well as different kinds of multilayers of Au/TM with transition metals TM = Fe, Co, Ni [440 142]. 

Mossbauer spectroscopy is particularly suitable to study ST since (1) the spectral parameters associated with the HS and LS states of iron(II) clearly differ and (2) the time-scale of the technique ( 10 s) allows the detection of the separate spin states in the course of the transition. Typically, Mossbauer spectra of HS iron(II) show relatively high quadrupole splitting (AEq 2-3 mm s ) and isomer shift (3 1 mm s ), while for LS iron(II), these parameters are generally smaller (AEq < 1 mm s 3 < 0.5 mm s ). Among the early applications of Mossbauer spectroscopy to study ST phenomena in iron(II) complexes is the work of Dezsi et al. [7] on [Fe (phen)2(NCS)2] (phen = 1,10-phenanthroline) as a function of temperature (Fig. 8.2). The transition from the HS ( 12) state (quadrupole doublet of outer two lines with AEq 3 mm s ) to the LS CAi) state (quadrupole... 

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