Chemically induced dynamic electron polarization. II. A general theory for radicals produced by photochemical reactions of excited triplet carbonyl compounds

Abstract

Electron spin resonance emission was observed from some photochemically produced semiquinone radicals in liquid isopropanol. It is proposed that the dynamic electron polarization is due to the optically spin polarized triplets of the parent quinones and their subsequent hydrogen abstraction reaction with retention of polarization in the resultant semiquinone radicals. Theoretical calculations have been carried out using typical zero field parameters for aromatic triplet molecules and the established assumption that the intersystem crossing rates to the three sublevels are unequal. Calculations reveal significant spin polarization of the triplets randomly oriented in an arbitrary magnetic field. Further treatment shows that when the triplet depolarization via relaxation is comparable to the chemical hydrogen abstraction rate, the resultant radical retains the polarization and is thus in the emissive mode.