U393060.pdf (5.35 MB)
Electron spin resonance studies of some silver, mercury, tin and lead complexes.
thesisposted on 2015-11-19, 08:47 authored by H. C. Starkie
This thesis is concerned with the study of silver, mercury, tin and lead containing radicals, formed by the low temperature ?-irradiation of either pure compounds of these elements or of frozen solutions containing these compounds, by the technique of electron spin resonance (e.s.r.). The first chapter introduces the technique of e.s.r. and covers the historical development of the technique, the relation of the electronic structure of the paramagnetic molecule to its experimental e.s.r. spectrum, factors effecting e.s.r. linewidths, experimental methods of e.s.r. and the interpretation of e.s.r. powder spectra.;The second chapter deals with the study of the electronic properties of impurity doped crystalline solids. The electronic structures of VK centres, silver atom and Ag2+ complexes, formed in irradiated alkali halides, were determined by e.s.r. and their subsequent reactions, upon warming up the samples, were studied by both e.s.r. and thermoluminescence techniques. The significance of these results for silver doped alkali halide systems and for silver halide systems are discussed.;The third chapter deals with the properties of some paramagnetic ions of silver, mercury, tin and lead. The properties of silver atoms on a silica gel surface, mercury ions formed in frozen, irradiated, solutions of mercury salts, the ions Sn3+ and Pb3+ in irradiated, pure, tin and lead salts, lead centres in irradiated, hydrated and anhydrous, plumbous acetate and some unidentified paramagnetic centres are discussed. Chapter four deals with the properties of alkyl and phenyl complexes of tin and lead. The ion PbMe2+, trialkyl tin and trialkyl lead radicals, trimethyl and triphenyl lead halide anions and some other, related, paramagnetic tin centres are discussed. The appandix discusses the methods used to calculate the e.s.r. parameters for systems with large nuclear hyperfine coupling constants.
Date of award1973-01-01
Awarding institutionUniversity of Leicester