Release Time:2019-03-10  Hits:

Indexed by: Journal Article

Date of Publication: 2009-01-01

Journal: JOURNAL OF THEORETICAL & COMPUTATIONAL CHEMISTRY

Included Journals: Scopus、SCIE

Volume: 8

Issue: SUPPL. 1

Page Number: 1073-1086

ISSN: 0219-6336

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

Abstract: 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.