Physical Sciences and Mathematics Commons^™

Theoretical Study Of Solvent Effects On The Electronic Coupling Element In Rigidly Linked Donor-Acceptor Systems, Robert J. Cave, Marshall D. Newton, Krishna Kumar, Matthew B. Zimmt

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The recently developed generalized Mulliken-Hush approach for the calculation of the electronic coupling matrix element for electron-transfer processes is applied to two rigidly linked donor-bridge-acceptor systems having dimethoxyanthracene as the donor and a dicarbomethoxycyclobutene unit as the acceptor. The dependence of the electronic coupling matrix element as a function of bridge type is examined with and without solvent molecules present. For clamp-shaped bridge structures solvent can have a dramatic effect on the electronic coupling matrix element. The behavior with variation of solvent is in good agreement with that observed experimentally for these systems.