Two particular aspects of solute dynamics in ordered media are analysed on the basis of the solution of multivariate diffusion equations: the effects of the solvation dynamics on the rotational motions of dipolar probes in liquid crystal solvents, and the alteration of reaction pathways in isomerization kinetics caused by the solvent order. The introduction of a suitable solvent coordinate allows the interpretation of high frequency contributions in the rotational correlation functions observed by spectroscopic techniques, namely dielectric dispersion, IR and Raman spectroscopy, ESR lineshapes and optical Kerr effect. For molecular systems undergoing conformational changes, a method is offered to evaluate the modification of the torsional barriers resulting from the anisotropic torques modulated by the molecular shape changes along the reaction coordinate.
Rotational dynamics and conformational kinetics in liquid crystals
FERRARINI, ALBERTA;POLIMENO, ANTONINO;NORDIO, PIER LUIGI
1993
Abstract
Two particular aspects of solute dynamics in ordered media are analysed on the basis of the solution of multivariate diffusion equations: the effects of the solvation dynamics on the rotational motions of dipolar probes in liquid crystal solvents, and the alteration of reaction pathways in isomerization kinetics caused by the solvent order. The introduction of a suitable solvent coordinate allows the interpretation of high frequency contributions in the rotational correlation functions observed by spectroscopic techniques, namely dielectric dispersion, IR and Raman spectroscopy, ESR lineshapes and optical Kerr effect. For molecular systems undergoing conformational changes, a method is offered to evaluate the modification of the torsional barriers resulting from the anisotropic torques modulated by the molecular shape changes along the reaction coordinate.
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