Journal of Physical Chemistry, Vol.100, No.50, 19412-19416, 1996
Picosecond Dynamics of Intermolecular Proton and Deuteron Transfer Between Benzophenone and N,N-Dimethylaniline
Picosecond absorption spectroscopy is used to study the dynamics of proton and deuteron transfer in the benzophenone/N,N-dimethylaniline contact radical ion pair in the solvents benzene and tetrahydrofuran. From temperature-dependent studies of this kinetic process, the energy of activation and A factors for proton and deuteron transfer are derived. These parameters are then analyzed within the classical and semiclassical models for proton transfer, the Borgis-Hynes model for proton transfer, and the two-step model developed by Kreevoy and Kotchevar for hydride transfer. We conclude that prior to proton transfer there is a rate-limiting reorganization of the contact radical ion pair complex that allows for the transfer of the proton.
Keywords:TRANSFER-REACTION-RATES;NONADIABATIC PROTON;ACETONITRILE SOLUTION;EXCITED BENZOPHENONE;TRANSFER KINETICS;LASER PHOTOLYSIS;HYDRIDE TRANSFER;SOLVENT;PHOTOREDUCTION;STATE