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Classical description of activated conformational processes in molecular systems coupled to solvent degrees of freedom
Author(s) -
Nordio P. L.,
Polimeno A.
Publication year - 1996
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/(sici)1097-461x(1996)60:1<321::aid-qua32>3.0.co;2-e
Subject(s) - chemistry , relaxation (psychology) , chemical physics , bistability , dissipative system , degrees of freedom (physics and chemistry) , non equilibrium thermodynamics , statistical physics , harmonic oscillator , molecular dynamics , computational chemistry , classical mechanics , physics , thermodynamics , quantum mechanics , psychology , social psychology
Extended Fokker‐Planck (FP) equations are generalized stochastic equations which describe the evolution of a set of coordinates, loosely referred to as solute , coupled with a relevant set of solvent variables. They are useful for the analysis of molecular dynamics in liquids, when a time‐scale separation between probe motions and relaxation times of interactions with surroundings particles cannot be performed, because of persistence of slowly fluctuating components. In this article, we focus attention on a model system, made up of an angular coordinate and its conjugate momentum, submitted to a bistable potential, and coupled to a dissipative harmonic mode, to investigate the influence of polar solvents on reactive dynamics. The results are appropriate to describe dielectric effects, solvent‐controlled conformational changes involving charge transfer which occur in photophysical processes, and the dynamic Stokes shifts observed in time‐resolved fluorescence experiments. © 1996 John Wiley & Sons, Inc.