Quantum chemical probes of electron-transfer kinetics: The nature of donor-acceptor interactions
- Brookhaven National Lab., Upton, NY (United States). Chemistry Dept.
The specific focus of this review is to survey recent progress in the application of theoretical and computational techniques of quantum chemistry to the elucidation of electronic factors controlling donor/acceptor interactions in electron-transfer reactions. The experimental data which provides the impetus for most of the theoretical work addressed here pertains predominantly to condensed-phase systems involving disorder (i.e., nonperiodic) media. For the most part the author is able to deal with models based on discrete molecular clusters (either large molecules or supermolecules) consisting of localized donor, acceptor, and intervening bridging sites. He confines his attention to cases of relatively weakly interacting donor/acceptor systems where, indeed, the occurrence of localized states may be safely assumed. The recent review of solid-state electron-transfer processes by Mikkelsen and Ratner dealt also with situations of more extended electronic states which may be important in periodic environments. As much as possible, the present review deals with purely electronic aspects of electron transfer, although attention is drawn to vibronic factors as deemed necessary. The overall goal of the review is to provide a unified picture of the combined capabilities of modern quantum chemistry in yielding accurate quantitative measures of the strength of electronic coupling and at the same time providing compact models for understanding the coupling in terms of the concepts of molecular bonding and electronic structure. The review should thus serve to complement other recent reviews which have dealt with electron-transfer kinetics on a broader basis. 98 refs., 4 figs., 6 tabs.
- DOE Contract Number:
- AC02-76CH00016
- OSTI ID:
- 7049732
- Journal Information:
- Chemical Reviews; (United States), Vol. 91:5; ISSN 0009-2665
- Country of Publication:
- United States
- Language:
- English
Similar Records
Examining Forster Energy Transfer for Semiconductor Nanocrystaline Quantum Dot Donors and Acceptors
Impact of Temperature and Non-Gaussian Statistics on Electron Transfer in Donor–Bridge–Acceptor Molecules