Hyperfine splitting properties

The ESR spectra of a large variety of sulfonyl radicals have been obtained photolytically in liquid phase over a wide range of temperature. Some selected data are summarized in Table 2. The magnitudes of hyperfine splittings and the observations of line broadening resulting from restricted rotation about the C—S bond have been used successfully in conjunction with INDO SCF MO calculations to elucidate both structure and conformational properties. Thus the spin distribution in these species is typical of (T-radicals with a pyramidal center at sulfur and in accord with the solid-state ESR data. 

Results obtained from the alkali iodides on the isomer shift, the NMR chemical shift and its pressure dependence, and dynamic quadrupole coupling are compared. These results are discussed in terms of shielding by the 5p electrons and of Lbwdins technique of symmetrical orthogonalization which takes into account the distortion of the free ion functions by overlap. The recoilless fractions for all the alkali iodides are approximately constant at 80°K. Recent results include hybridization effects inferred from the isomer shifts of the iodates and the periodates, magnetic and electric quadrupole hyperfine splittings, and results obtained from molecular iodine and other iodine compounds. The properties of the 57.6-k.e.v. transition of 1 and the 27.7-k.e.v. transition of 1 are compared. 

Esr spectroscopy has been used extensively in connection with the problem of radical stabilization. Two properties of the radicals are analysed to obtain information on their stability spin-density distribution and lifetime. The former has a solid physical basis in hyperfine splitting and the universally accepted hypothesis that spin delocalization accords stability to a free radical (for a discussion, see Walton, 1984). The more the unpaired spin density is delocalized, the higher is, supposedly, the stability of the radical. This argument, as we shall see, is mainly used on a qualitative basis (see. 

These radical adducts have characteristic resolved ESR spectra which allow the accurate identification of all magnetic properties (g-factors and hyperfine splitting of all magnetic nuclei of the system including 13C, 73Ge and 117Sn and 119Sn of the observed species)33. 

In the case of the positronium spectrum the accuracy is on the MHz-level for most of the studied transitions (Is hyperfine splitting, Is — 2s interval, fine structure) [13] and the theory is slightly better than the experiment. The decay of positronium occurs as a result of the annihilation of the electron and the positron and its rate strongly depends on the properties of positronium as an atomic system and it also provides us with precise tests of bound state QED. Since the nuclear mass (of positronium) is the positron mass and me+ = me-, such tests with the positronium spectrum and decay rates allow one to check a specific sector of bound state QED which is not available with any other atomic systems. A few years ago the theoretical uncertainties were high with respect to the experimental ones, but after attempts of several groups [17,18,19,20] the theory became more accurate than the experiment. It seems that the challenge has been undertaken on the experimental side [13]. 

Factors such as solvation and, in the case of ion-radicals, the counterion, may influence the properties of radicals. It is beyond the scope of this chapter to describe ion aggregation mechanisms and the factors which govern the hyperfine splittings manifested by counterions. The subject has been reviewed, however, by a prime mover in the field.12 Suffice it to say that the association of an ion-radical with a counterion may lead to a considerable redistribution of spin within the radical with consequences for the chemistry. For example, disproportionation equilibria and persistence may be influenced by the nature of the association.68 Closely allied to the phenomenon of ion association is, of course, solvation. Whether or not an ion-pair or other ionic assemblage exists in preference to free ions depends on the extent of the solvation of the ions. Nonionic radicals are also subject to variation in properties with change in solvent principally owing to interaction of the solvent with dipolar charges within the radical. 

Both the g-value distribution and the hyperfine splittings of the g = 2.0055 defect are consistent with the expected properties of dangling bonds. Consistency, however, does not constitute proof of the structure, and other possibilities have been proposed, which are discussed below. The ESR parameters do provide quantitative constraints that must be met by alternative models and, at present, are the only specific experimental information that we have about the defect wavefunctions. 

For some other molecular properties the wave function must be accurate in the proximity of nuclei. Such a property is for example the hyperfine splitting caused by Fermi contact term which is proportional to the total spin density at the nucleus. Among the one-electron pro-... 

Low-spin Fe(iii) porphyrins have been the subject of a number of studies. (638-650) The favourably short electronic spin-lattice relaxation time and appreciable anisotropic magnetic properties of low-spin Fe(iii) make it highly suited for NMR studies. Horrocks and Greenberg (638) have shown that both contact and dipolar shifts vary linearly with inverse temperature and have assessed the importance of second-order Zeeman (SOZ) effects and thermal population of excited states when evaluating the dipolar shifts in such systems. Estimation of dipolar shifts directly from g-tensor anisotropy without allowing for SOZ effects can lead to errors of up to 30% in either direction. Appreciable population of the excited orbital state(s) produces temperature dependent hyperfine splitting parameters. Such an explanation has been used to explain deviations between the measured and calculated shifts in bis-(l-methylimidazole) (641) and pyridine complexes (642) of ferriporphyrins. In the former complexes the contact shifts are considered to involve directly delocalized 7r-spin density... 

Isotope Shift. Further information comes from isotope shift, illustrated in Figure 6 for a line of U I. In an empirical term analysis the isotope shift of a level can be considered a characteristic property in the same way as the g-value or hyperfine splitting. One cannot determine the isotope shifts of the two levels involved in a transition from the one... 

The blue copper proteins or cupredoxins are a group of proteins that exhibit a number of unusual properties, viz. a bright blue colour, a narrow hyperfine split-... 

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