Solvent Dynamical Effects in Electron Transfer: Some Predicted Modifications in the Presence of Reactant Vibrational Activation and Comparisons With Experimental Findings.
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.
Document Details
- Document Type
- Technical Report
- Publication Date
- May 01, 1992
- Accession Number
- ADA251415
Entities
People
- D. K. Phelps
- Michael J. Weaver
Organizations
- Purdue University