Solvent Relaxation in Thermal Electron-Transfer Reactions: Some Comparisons with Real-Time Measurements of Solvation Dynamics.

Abstract

The role of solvent dielectric relaxation on the barrier-crossing dynamics for outersphere electron transfer (ET), as evaluated from the solvent-dependent kinetics of metallocene self-exchange reactions, is compared with recent real-time measurements of polar solvation dynamics obtained from time-dependent fluorescence Stokes shifts (TDFS) for suitable charge-transfer excited states. While the solvent-dependent kinetics obtained in some aprotic media are consistent with the TDFS measurements, the barrier-crossing dynamics in several associated and/or highly polar liquids are indicative of much faster relaxation than inferred from TDFS. The possible nature, and implications, of these rapid modes are discussed. Keywords: Solvent relaxation, Electron transfer, Time resolved fluorescence.

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Document Details

Document Type
Technical Report
Publication Date
Feb 17, 1988
Accession Number
ADA190146

Entities

People

  • George E. Mcmanis
  • Michael J. Weaver

Organizations

  • Purdue University

Tags

Communities of Interest

  • Advanced Electronics
  • Materials and Manufacturing Processes

DTIC Thesaurus Topics

  • Alcohols
  • Carbonate Esters
  • Charge Transfer
  • Chemical Reactions
  • Chemical Synthesis
  • Chemistry
  • Classification
  • Dielectric Permittivity
  • Dielectric Properties
  • Electron Transfer
  • Exchange Reactions
  • Frequency
  • Military Research
  • Organic Chemistry
  • Plastic Explosives
  • Relaxation Time
  • Three Dimensional

Fields of Study

  • Chemistry

Readers

  • Electrochemical Surface Science
  • Molecular Photonics/Laser Physics

Technology Areas

  • AI & ML
  • Microelectronics