Accession Number : ADA266061


Title :   Solvent Dynamical Effects in Electron Transfer: Molecular Dynamics Simulations of Reactions in Methanol


Descriptive Note : Technical rept.


Corporate Author : PURDUE UNIV LAFAYETTE IN DEPT OF CHEMISTRY


Personal Author(s) : Phelps, Donald K ; Weaver, Michael J ; Ladanyi, Branka M


Full Text : https://apps.dtic.mil/dtic/tr/fulltext/u2/a266061.pdf


Report Date : Apr 1993


Pagination or Media Count : 39


Abstract : Molecular-dynamics simulations of activated electron-transfer (ET) reactions in methanol have been undertaken in order to explore the physical nature of the solvent dynamics coupled to ET barrier crossing, and to probe some underlying reasons for the facile kinetics observed in this solvent. The reactant is modeled by a pair of Lennard-Jones (LJ) spheres in contact, of varying diameter (4 or 5 A), and containing a univalent charge (cation or anion) on one site so to probe possible effects of the ionic charge sign. Following equilibration, the collective solvent response to a sudden charge transfer between the spherical sites is followed, and described in terms of the response function C(t), describing the difference in the solvent-induced electrostatic potential between the initial and final solute states. In all cases, the C(t) curves exhibit a very rapid (50-100 fs) initial decay component associated with hydroxyl inertial motion, followed by components arising from hydrogen-bond librational and diffusive motions


Descriptors :   *SOLVENTS , *KINETICS , *ELECTRON TRANSFER , SIMULATION , CATIONS , DIAMETERS , HYDROGEN BONDS , DYNAMICS , SITES , ELECTROSTATICS , ANIONS , DECAY , CROSSINGS , MOTION , RESPONSE , METHANOLS , SOLUTES , BARRIERS , CHARGE TRANSFER


Subject Categories : Physical Chemistry


Distribution Statement : APPROVED FOR PUBLIC RELEASE