Modeling donor/acceptor interactions: Combined roles of theory and computation

摘要

An extended superexchange model for electron transfer (ET) matrix elements (H-DA) 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 pi and sigma electronic manifolds for different distributions of phenylene torsion angles is analyzed in detail. (C) 2000 John Wiley & Sons, Inc. [References: 38]