Mossbauer parameters

Table 15.4 and Fe Mossbauer parameters of Cu5.47Fe2.9Sn13.1S32. 

Bis(imino)pyridine iron complex 5 as a highly efficient catalyst for a hydrogenation reaction was synthesized by Chirik and coworkers in 2004 [27]. Complex 5 looks like a Fe(0) complex, but detailed investigations into the electronic structure of 5 by metrical data, Mossbauer parameters, infrared and NMR spectroscopy, and DFT calculations established the Fe(ll) complex described as 5 in Fig. 2 to be the higher populated species [28]. 

Table IV. Mossbauer Parameters for Sulfided C0-M0/AI2O3 Catalysts.

Figure 2A. Schematic diagram of Mossbauer parameters isomer shift (6), quadrupole splitting (AEq) and magnetic dipole splitting of the nuclear energy states of 57pe leading to various hyperfine splitting in Mossbauer spectra.

In addition to the four detectors used to detect backscattered radiation from the sample, there is a fifth detector to measure the transmission spectrum of the reference absorber (a- Fe, a- Fe203, Fc304 see Fig. 3.16). Sample and reference spectra are recorded simultaneously, and the known temperature dependence of the Mossbauer parameters of the reference absorber can be used to give a measurement of the average temperature inside the SH, providing a redundancy to measurements made with the internal temperature sensor (see Sect. 3.3.4). 

During the mission, the magnetite CCT was measured in several runs to verify the functionality of MIMOS II. The well-known Mossbauer parameters of magnetite were used for velocity calibration, as shown in Fig. 3.22 for different temperatures. This kind of measurement was done in the laboratory with the flight units as a function of temperature to be used as a reference for the measurements on Mars. Figure 3.22 shows the Mossbauer spectra of the CCT at different mean temperatures. 

However, useful as it is, ligand field theory is not a predictive first principles theory. Thus, it cannot be used to predict a priori the Mossbauer parameters of a given compound. Yet, the need to do so arises fi equently in Mossbauer spectroscopy. For example, if a reaction intermediate or some other unstable chemical species has been characterized by freeze quench Mossbauer spectroscopy and its SH parameters become available, then the question arises as to the structure of the unstable species. Mossbauer spectroscopy in itself does not provide enough information to answer this question in a deductive way. However, the more modest question which structures are compatible with the observed Mossbauer parameters can be answered if one is able to reliably predict Mossbauer parameters... 

There may, however, be a number of other reasons to pursue a predictive first principles theory of Mossbauer spectroscopy. For example, one may want to elucidate structure/spectroscopy correlations in the cleanest way. To this end one may construct in the computer a number of models with systematic variations in oxidation states, spin states, coordination numbers, and identity of hgands to name only a few chemical degrees of freedom. In such studies it is immaterial whether these molecules have been made or could be made what matters is that one can find out which structural details the Mossbauer parameters are most sensitive to. This can provide insight into the effects of geometry or covalency that are very difficult to obtain by any other means. 

In 1970, Charlton and Nichols [340] published their results of a Au Mossbauer study on 31 gold complexes, for which they describe a general correlation between Mossbauer parameters and chemical features. They investigated the series... 

Table 7.15 Mossbauer parameters observed for various gold compounds at 4.2 K. The...

Coordination compounds of dianionic dithiolene (S2C2 R2) and benzene-1,2-dithiolene (bdt = (S2C6H4) and their derivatives have been studied since the 1960s by Mossbauer spectroscopy [87] and other techniques. Nevertheless, many aspects of their electronic structure remained uncertain for a long time. The five-coordinate ferric complexes with two equatorial dithiolene ligands exhibit intermediate spin and show the Mossbauer parameters = 0.25-0.38 mm s and A q = 1.6-3.2 mm s For example, [Fe° mnt)2/ y] with two mnt ligands (=S2C2(CN)2) and an... 

Table 8.1 Mossbauer parameters of five- and six-coordinate ferric compounds with 5pe = 3/2...

Table 8.2 Mossbauer parameters of some five- and the first truly four-coordinate ferric porphyr-inates with admixed spin S = (3/2, 5/2)...

Table 8.3 Mossbauer parameters of iron(II) complexes with intermediate spin (S = 1)...

Table 8.5 Mossbauer parameters of iron(V) and ironfVI) compounds ...

---