Within a given simple model hamiltonian of extended Hiickel, Hubbard or CNDO type, we derive, using perturbation theory, an expression for the effective transfer rate of an electron or hole from one region within the molecule to another. Vibronic interactions, though crucial to the real, observed rate process, are ignored for present purposes; rather, attention is focused on comparative electronic effects. Perturbation theory is used to derive relations for effective transfer integrals. Application to mixed valence dimeric systems as well as to substituted biphenyl derivatives is suggested. Brief comparison with other treatments is outlined.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Molecular Biology
- Condensed Matter Physics