Exact analysis of polycrystalline electron spin echo envelope modulation including mutual nuclear arrangements and quadrupole interactions and its application to methyl radicals in irradiated crystals of lithium acetate dihydrate

Abstract

The method of exact analysis including mutual nuclear arrangements and quadrupole interactions is developed for electron spin echo envelope modulation (ESEM) from polycrystalline samples using the formulation in an arbitrary laboratory coordinate system, which makes it possible to perform an exact angular integration. In order to assess polycrystalline ESEM by comparing with electron nuclear double resonance (ENDOR) data, the method is applied to analyze deuterium hyperfine modulation on the two-pulse electron spin echo (ESE) envelope decay observed for methyl radicals radiolytically produced in CD3COOLi ⋅ 2H2O and CH3COOLi ⋅ 2D2O. The results are totally consistent with our previous study by single crystal 1H ENDOR. Through this application, importance of the nuclear quadrupole term is also shown based on the exact method. The rigid deuterons in the water of crystallization show a marked quadrupole effect as compared with those in the freely rotating CD3 group. The contributions from the distant nuclei to the modulation pattern are also studied by the exact method using the crystallographic data. We have further clarified that the origin of the disagreement of a previous Li ESEM with our ENDOR is mainly in the use of a unit spin density on the spin probe despite its reduction by delocalization to the environment.