title: A one-dimensional energy diffusion approach to multidimensional dynamical processes in the condensed phase.
abstract: We propose a generalized one-dimensional energy diffusion approach for describing the dynamics of multidimensional dynamical processes in the condensed phase. On the basis of a formalism originally due to Zwanzig, we obtain a one-dimensional kinetic equation for a properly selected relevant dynamical quantity and derive new analytical results for the dynamics of a multidimensional electron-transfer process, nonequilibrium solvation, and diffusive escape from a potential well. The calculated results for electron-transfer reactions in solvent-separated and contact ion pair systems are found to be in good agreement with the experimental results. We are able to explain the rate of the electron-transfer reaction using much smaller and reasonable values of the solvent reorganization energy in contrast to earlier works that had to use a much larger value. The proposed theory is not only conceptually simpler than the conventional approaches but is also free from many of their limitations. More importantly, it provides a single theoretical framework for describing a wide class of dynamical phenomena.
authors.affiliation: Theoretical Chemistry Section, Bhabha Atomic Research Centre, Mumbai 400 085, India.
authors.forename: Alok
authors.initials: A
authors.lastname: Samanta
authors.forename: Swapan K
authors.initials: SK
authors.lastname: Ghosh
mesh_terms: D055598:Chemical Phenomena; D002627:Chemistry, Physical; D004058:Diffusion; D004583:Electrons; D004735:Energy Transfer; D007700:Kinetics; D008956:Models, Chemical; D013997:Time Factors