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论文类型：期刊论文

发表时间：2009-01-01

发表刊物：JOURNAL OF THEORETICAL & COMPUTATIONAL CHEMISTRY

收录刊物：SCIE、Scopus

卷号：8

期号：SUPPL. 1

页面范围：1073-1086

ISSN号：0219-6336

关键字：Excited-state intramolecular electron transfer; excited-state intramolecular proton transfer; 2D site and 3D cube representations

摘要：In this paper, the two-dimensional (2D) site and the three-dimensional (3D) cube representations [Sun MT, J Chem Phys 124: 054903, 2006] have been further developed to study the charge transfer during excited-state relaxation. With these newly developed representations, we theoretically investigate the excited-state intramolecular electron transfer (ESIET) in enol excited-state geometry relaxation, and ESIET coupled with excited-state intramolecular proton transfer (ESIPT) in phototautomerization (in enol to keto transformation). The energy levels of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of HBODC in enol and keto absorption and fluorescence are compared to understand photoinduced ESIET and ESIPT process. The excited regions of molecule (where arrangement of electron density takes place during excited-state relaxation) are located with 2D site representation. 3D cube representations visualize the character of charge transfer (CT) in those regions. Results of the research indicate that the ability of charge transfer during enol excited-state geometry relaxation is much stronger than that in phototautomerization.