Accession Number:

ADA265886

Title:

Molecular Solvent-Dynamical Effects on Activated Electron-Transfer Kinetics: How Important is Solvent Friction

Descriptive Note:

Technical rept.,

Corporate Author:

PURDUE UNIV LAFAYETTE IN DEPT OF CHEMISTRY

Personal Author(s):

Report Date:

1993-04-01

Pagination or Media Count:

26.0

Abstract:

The likely extent of retardation exerted by solvent friction upon the rates of activated electron-transfer ET processes is explored and evaluated with reference to some extent solvent-dependent data for metallocene ET self exchanges. Barrier-crossing frequencies extracted from the experimental kinetic and barrier data for suitably adiabatic reactions are compared with solvent inertial frequencies i.e. the zero-friction limit as estimated from currently available analytic expressions. The additional extent of rate retardation seen in going from low-friction to ostensibly strongly overdamped solvents as deduced in this manner is seen to be substantially muted in comparison with the predictions of conventional Debye-continuum approaches, although follows a solvent functionality that is nevertheless roughly in accord with the latter. The likely importance of more rapid dynamics associated with short-range molecular solvation is addressed in the light of these findings. Author

Subject Categories:

  • Physical Chemistry
  • Atomic and Molecular Physics and Spectroscopy
  • Mechanics
  • Solid State Physics

Distribution Statement:

APPROVED FOR PUBLIC RELEASE