| Abstract
| - In this work we address the interpretation, via an ab initio integrated computational approach, ofcontinuous wave electron spin resonance (cw-ESR) spectra of p-(methylthio)phenyl nitronylnitroxide(MTPNN) dissolved in toluene. Our approach is based on the determination of the spin Hamiltonian,averaged with respect to fast vibrational motions, with magnetic tensor parameters (Zeeman and hyperfinetensors) characterized by quantum mechanical density functional calculations. The system is then describedby a stochastic Liouville equation, with inclusion of diffusive rotational dynamics. Parametrization of diffusionrotational tensor is provided by a hydrodynamic model. Cw-ESR spectra of MTPNN are simulated for awide range of temperatures (155−292 K) with minimal resorting to fitting procedures, proving that thecombination of sensitive ESR spectroscopy and sophisticated modeling can be highly helpful in providingstructural and dynamic information on molecular systems.
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