Accession Number : ADA251415

Title :   Solvent Dynamical Effects in Electron Transfer: Some Predicted Modifications in the Presence of Reactant Vibrational Activation and Comparisons With Experimental Findings.

Descriptive Note : Technical rept.,

Corporate Author : PURDUE UNIV LAFAYETTE IN DEPT OF CHEMISTRY

Personal Author(s) : Phelps, D. K. ; Weaver, M. J.

Report Date : MAY 1992

Pagination or Media Count : 27

Abstract : The predicted alterations in the solvent-dependent reaction dynamics of electron-transfer processes brought about by the presence of reactant vibrational (inner-shell) activation in addition to overdamped solvent motion are examined by using a slightly modified from of the theoretical treatment due to Sumi, Nadler, and Marcus. Allowance is made for the occurrence of nuclear tunneling involving the high-frequency vibrational modes, and for barrier crossing driven by solvent inertial polarization as well as vibrational activation. The latter enables the emergence of the zero-friction (transition-state theory, TST) limit to be included along with providing a unified description in the absence and presence of vibrational activation. Attention is focussed on the calculated dependencies of the reaction rate constant, and barrier-crossing frequency, upon the overdamped solvent relaxation time, over a range of parameters and in a format which can be compared directly with experimental solvent-dependent kinetic data.

Descriptors :   *SOLVENTS, *DYNAMICS, *ELECTRON TRANSFER, *PREDICTIONS, *EXPERIMENTAL DATA, *NITROBENZENES, *BENZONITRILES, *NITROMETHANE, *ACETONES, *ACETONITRILE, MOLECULAR STATES, COMPARISON, NUCLEAR PROPERTIES, DIPOLES, TUNNELING, HIGH FREQUENCY, INERTIAL SYSTEMS, POLARIZATION, KINETICS.

Subject Categories : Solid State Physics
      Solvents, Cleaners, and Abrasives
      Physical Chemistry
      Mechanics

Distribution Statement : APPROVED FOR PUBLIC RELEASE