Electron spin resonance studies of radiation effects. Final report, 1964-1979 (including annual progress reports for 1978 and 1979)

Abstract

The discovery of new free radicals, largely in irradiated single crystals of nonmetallic solids, and the determination of the molecular and electronic structures of these paramagnetic species by electron spin resonance (ESR) spectroscopy, have been carried out using a wide variety of organic and inorganic materials. The mechanisms of production of radicals in solids, their motions, and their reactions have been investigated and some applicable general principles deduced. Emphasis has been on aliphatic free radicals from irradiated carboxylic acids and amides and their halogen-substituted derivatives, organometallic radicals and substituted cyclic hydrocarbon radicals; inorganic radicals studied include V centers, hypervalent radicals and electron adducts. Extensive investigations of paramagnetic transition metal complexes, particularly cyanides and fluorides, have been made. In all cases quantum mechanical calculations have been employed as far as possible in interpreting the data. An improved method for analyzing experimental ESR spectra of single crystals has been developed and a number of crystal structures have been determined to supplement the ESR studies. Applications of nuclear quadrupole resonance spectroscopy to the study of structure and bonding in inorganic solids have been made and a method for using nuclear magnetic relaxation data for estimating quadrupole coupling constants in liquids has been developed.