Journal of Physical Chemistry B, Vol.119, No.46, 14728-14737, 2015
Extension of Hopfield's Electron Transfer Model To Accommodate Site-Site Correlation
Extension of the Forster analogue for the ET rate constant (based on intermediate electron detachment or attachment states) with inclusion of site-site correlation Clue to coulomb terms associated with solvent reorganization energy and the, driving force, has been developed and illustrated for a simple three state, two mode model The model is applicable to charge separation (CS), recombination (CR), and shift (CSh) ET processes, with or without an intervening bridge The model provides a unified perspective on the role of virtual intermediate states in accounting for the thermal Franck-Condon weighted density of states (FCWD), the gaps controlling superexchange coupling, and,mean absolute redox potentials, with full accommodation of site-site coulomb interactions. Two types of correlation have been analyzed: aside from the site-site correlation due to Coulomb interactions, we have emphasized the intrinsic "nonorthogonality" which generally pertains to reaction coordinates (RCs) for different Et processes: involving multiple electronic states, as may be expressed by suitably,defined direction,cosines (cos(theta)). A pair of RCs may be nonorthogonal even when the site-site coulomb correlations., are absent. While different RCs are linearly independent in the Mathematical sense for all theta not equal 0 degrees, they are independent in the sense of being "uncorrelated" only in the limit of orthogonality (theta = 90 degrees). Application to more than two coordinates is straightforward and may include both discrete and continuum contributions.