ELECTRON-TRANSFER RATES FROM TIME-DEPENDENT CORRELATION-FUNCTIONS - WAVEPACKET DYNAMICS, SOLVENT EFFECTS, AND APPLICATIONS

The golden-rule expression for the non-adiabatic electron-transfer rat e constant in donor/acceptor systems is analyzed using a Fourier (time -dependent) representation. The rate constant is written in terms of a n evolving overlap of wavepackets on initial and final state potential -energy surfaces. By following the explicit time-dependence of these f unctions, we can obtain both standard results of electron-transfer the ory for the specific case of a standard polaron-type model (including inverted-region behavior, temperature dependence, nuclear tunneling ef fects, energy sharing) and some important generalizations, including s ituations of breakdown of the Condon approximation, analysis of the ef fects of frequency changes, and simplifications of the relevant vibrat ional modes due to solvent, to intra-molecular vibrations, or to both. The correlation-function method is briefly described, and results of a number of calculations are discussed. Analysis includes the effects of inhomogeneous broadening and of energy flow into solvent and vibrat ional degrees of freedom. Analysis of two particular cases, subjects o f recent elegant experimental investigation, are included to show the applicability of the technique.