Accession Number : ADA190146

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

Descriptive Note : Technical rept.,

Corporate Author : PURDUE UNIV LAFAYETTE IN DEPT OF CHEMISTRY

Personal Author(s) : McManis, George E ; Weaver, Michael J

PDF Url : ADA190146

Report Date : 17 Feb 1988

Pagination or Media Count : 19

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.

Descriptors :   *ELECTRON TRANSFER, *FLUORESCENCE, *SOLVATION, *REACTION KINETICS, *CHROMOPHORES, DIELECTRICS, LIQUIDS, MEASUREMENT, POLAR REGIONS, REAL TIME, RELAXATION, SHIFTING, SOLVENTS, THERMAL PROPERTIES, TIME DEPENDENCE, STOKES RADIATION

Subject Categories : Physical Chemistry
      Radiation and Nuclear Chemistry

Distribution Statement : APPROVED FOR PUBLIC RELEASE