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) : Weaver, Michael J


Full Text : https://apps.dtic.mil/dtic/tr/fulltext/u2/a265886.pdf


Report Date : Apr 1993


Pagination or Media Count : 26


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)


Descriptors :   *SOLVENTS , *KINETICS , *FRICTION , *ELECTRON TRANSFER , *MOLECULAR PROPERTIES , FREQUENCY , ACTIVATION , DYNAMICS , RETARDATION , ADIABATIC CONDITIONS , SOLVATION , CROSSINGS , INERTIAL SYSTEMS , DAMPING , RATES , BARRIERS


Subject Categories : Physical Chemistry
      Atomic and Molecular Physics and Spectroscopy
      Mechanics
      Solid State Physics


Distribution Statement : APPROVED FOR PUBLIC RELEASE