Abstract
A 250-GHz electron paramagnetic resonance (EPR) study of the slow rotational diffusion of two spin probes in toluene, viz., perdeuterated 2,2,6,6-tetramethyl-4-piperidone (PDT) and 3-doxylcholestane (CSL) is presented. EPR spectra were obtained in the slow-motional and near-rigid limit regions, which corresponds to rotational correlation times 10 -10 >τ R >10 -6 s. These two probes differ significantly in size and shape, permitting a detailed exploration of the sensitivity of 250-GHz EPR to different aspects of the molecular dynamics such as rotational anisotropy and non-Brownian diffusion. Nonlinear least-squares fitting based on full stochastic Liouville calculations provides a sensitive means for discriminating amongst motional models
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