Electron spin resonance of symmetrical three-spin systems in nematic liquid crystals

An E.S.R. line-shape model is developed for fast tumbling three-spin systems in nematic liquid crystals. The line positions are calculated from a spin hamiltonian, which considers Zeeman, exchange, dipolar and hyperfine interactions of the three unpaired electrons. The dominant spin relaxation process, determining the line-widths, is assumed to result from the anisotropy of the zero-field splitting coupled to the molecular motion. The predictions of the theory are tested by comparison with the temperature-dependent E.S.R. spectra of trisverdazyl radicals in 4,4′-azoxydianisole. Good agreement is found between experimental and simulated spectra. A detailed analysis provides values for the solute order parameters Pbar] ₂ and Pbar] ₄. They correspond surprisingly well to predictions of the molecular-field theories of nematic liquid crystals.