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

✍ Scribed by Marshall D. Newton

• Publisher: John Wiley and Sons
• Year: 2000
• Tongue: English
• Weight: 504 KB
• Volume: 77
• Category: Article
• ISSN: 0020-7608
• DOI: 10.1002/(sici)1097-461x(2000)77:1<255::aid-qua23>3.0.co;2-o

✦ Synopsis

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 H DA 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.