標題: Ab initio characterization of electron transfer coupling in photoinduced systems: Generalized Mulliken-Hush with configuration-interaction singles
作者: Chen, HC
Hsu, CP
應用化學系分子科學碩博班
Institute of Molecular science
公開日期: 29-Dec-2005
摘要: To calculate electronic couplings for photoinduced electron transfer (ET) reactions, we propose and test the use of ab initio quantum chemistry calculation for excited states with the generalized Mulliken-Hush (GMH) method. Configuration-interaction singles (CIS) is proposed to model the locally excited (LE) and charge-transfer (CT) states. When the CT state couples with other high lying LE states, affecting coupling values, the image charge approximation (ICA), as a simple solvent model, can lower the energy of the CT state and decouple the undesired high-lying local excitations. We found that coupling strength is weakly dependent on many details of the solvent model, indicating the validity of the Condon approximation. Therefore, a trustworthy value can be obtained via this CIS-GMH scheme, with ICA used as a tool to improve and monitor the quality of the results. Systems we tested included a series of rigid, sigma-linked donor-bridge-acceptor compounds where "through-bond" coupling has been previously investigated, and a pair of molecules where "through-space" coupling was experimentally demonstrated. The calculated results agree well with experimentally inferred values in the coupling magnitudes (for both systems studied) and in the exponential distance dependence (for the through-bond series). Our results indicate that this new scheme can properly account for ET coupling arising from both through-bond and through-space mechanisms.
URI: http://dx.doi.org/10.1021/jp053712q
http://hdl.handle.net/11536/12951
ISSN: 1089-5639
DOI: 10.1021/jp053712q
期刊: JOURNAL OF PHYSICAL CHEMISTRY A
Volume: 109
Issue: 51
起始頁: 11989
結束頁: 11995
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