Dynamics of charge transfer chemical reactions in a polar medium within the scope of the Born-Kirkwood-Onsager model

• Published in: Chemical physics Vol. 157; no. 3; pp. 327 - 344
• Main Authors: Basilevsky, M.V., Chudinov, G.E.
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 15.11.1991; Elsevier
• Subjects: Chemistry; Exact sciences and technology; General and physical chemistry; Theory of reactions, general kinetics; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; Theoretical study; Solvation; Chemical reaction; Charge transfer; Polar solvent
• ISSN: 0301-0104
• DOI: 10.1016/0301-0104(91)89026-7

A theoretical scheme designed for the dynamical treatment of charge transfer chemical reactions in polar solvents within the scope of the Born-Kirkwood-Onsager model (BKO) is proposed. According to the BKO model a medium is considered as a uniform continuum where a cavity containing a chemical subsystem is cut out. The continuum representation of the medium implies a complex function for the dielectric permittivity ϵ(ω), being the only specific property of the medium. An inertial polarization field Φ in is used as a medium variable. A procedure of separation of the noninertial polarization is developed using the BKO model. A free energy functional is introduced which may be considered as an energy surface of the united “chemical subsystem+medium” system both for equilibrium and non-equilibrium realizations of the polarization field. The equation determining equilibrium realizations of the inertial field Φ in in the nonlinear case, when the charge distribution of the chemical subsystem depends on the medium polarization, is obtained on the basis of the variational principle. Starting from this equation a dynamical equation describing the temporal evolution of the charge transfer process is derived.