Modeling Donor/Acceptor Interactions: Combined Roles of Theory and Computation

Abstract

An extended superexchange model for electron transfer (ET) matrix elements (HDA) has been formulated as a superposition of McConnell-type pathways and implementated by combined use of configuration interaction wave functions (obtained using the INDO/s model of Zerner and co-workers) and the generalized Mulliken-Hush formulation of charge-localized diabatic states. Applications are made for et (and hole transfer) in several donor/bridge/acceptor radical anion (and cation) systems, (DBA)±, allowing detailed comparison with experimental HDA estimates. For the case of oligo phenylene ethynylene (OPE) bridges, the role of π and σ electronic manifolds for different distributions of phenylene torsion angles is analyzed in detail. © 2000 John Wiley & Sons, Inc.