Electron transfer integral between two zero-overlap states

• Published in: Journal of computational chemistry Vol. 17; no. 9; pp. 1108 - 1111
• Main Authors: Li, Xiang-Yuan, Tian, An-Min, He, Fu-Cheng, Yan, Guo-Sen
• Format: Journal Article
• Language: English
• Published: New York John Wiley & Sons, Inc 15.07.1996
• ISSN: 0192-8651; 1096-987X
• DOI: 10.1002/(SICI)1096-987X(19960715)17:9<1108::AID-JCC3>3.0.CO;2-W

In the research of electron transfer (ET) reactions, the theoretical calculation of the ET matrix element VBA is of special importance. Some examples in which the two electron‐localized states have a zero overlap were found. Thus, a new procedure for VBA calculation was developed and applied to the investigation of the donor‐acceptor 90° oriented ET reactions. This procedure, which is a supplement necessary to the recently developed approach suitable for a nonorthogonal case, was derived in detail. To check the rationality of the zero value of VBA in the reaction O2O−2 → O−2O2, the angle dependence of SBA and VBA between two electron‐localized states was calculated. © 1996 by John Wiley & Sons, Inc.