Theory of solvent influence on reaction dynamics.
A generalization of the recently published quantum-classical approximation [A. A. Neufeld, J. Chem. Phys., 119, 2488 (2003)] for the purposes of reaction dynamics in condensed phase is presented. The obtained kinetic equations treat a solvent influence in a nonphenomenological way, account for the change of the free energy of the surrounding media, allow for different solvent dynamics in each reaction channel, and constitute a powerful framework for an accurate modeling of solvent effects, including ultrafast processes. The key features of the approach are its differential form, which considerably facilitates practical applications, and well defined wide applicability limits. The developed methodology fully accounts for an arbitrary long memory of the canonical bath and covers solvent-induced processes from a subpicosecond time scale.
Neufeld
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Abteilung für Spektroskopie und Photochemische Kinetik, Max-Planck-Institut für Biophysikalische Chemie, Am Fassberg, D-37077 Göttingen, Germany. aneufel@gwdg.de
D007700:Kinetics; D008968:Molecular Conformation; D011789:Quantum Theory; D012996:Solutions / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry*; D013816:Thermodynamics
D012996:Solutions; D012997:Solvents