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dc.contributor.authorXu, Xuefeizh_CN
dc.contributor.authorZhang, Ruiqinzh_CN
dc.contributor.authorCao, Zexingzh_CN
dc.contributor.author曹泽星zh_CN
dc.contributor.authorZhang, Qianerzh_CN
dc.contributor.author张乾二zh_CN
dc.date.accessioned2011-04-26T08:04:11Z
dc.date.available2011-04-26T08:04:11Z
dc.date.issued2008zh_CN
dc.identifier.citationJOURNAL OF THEORETICAL & COMPUTATIONAL CHEMISTRY,2009,7(4):719-736zh_CN
dc.identifier.issn0219-6336zh_CN
dc.identifier.urihttp://dx.doi.org/doi:10.1142/S0219633608004088zh_CN
dc.identifier.urihttps://dspace.xmu.edu.cn/handle/2288/2707
dc.description.abstractStructures and properties of the low-lying states in 4-(dicyanomethylene)-2-methyl-6(p-dimethylaminostyryl)-4H-pyran (DCM) have been investigated theoretically. Calculations show that the dimethylamino and dimethylanilino twisted conformations of DCM on the potential energy surface of the first excited state (S-1) have relatively high stabilities and remarkable intramolecular charge transfers (ICT). Both structures can serve as candidates for the red-shifted emissive state in polar solvent. In particular, the dimethylanilino twisted ICT state has been predicted to have a dipole moment increment of 20 Debye with respect to the ground state by CASSCF calculations, in good agreement with the suggested experimental values. The optimized geometry of the S-1 state exhibits a long central CC bond of 1.458 angstrom, which makes the trans-cis isomerization quite facile through intramolecular rotation around the central CC bond on the S-1 potential surface. The S-1 state is a precursor to the formation of the ICT emissive state and photoinduced trans cis isomerization. The S-1/S-0 crossing in polar solvent and avoid-crossing in the gas phase as well as in non-polar solvent are involved in the trans-cis isomerization process. The presence of an early S-1/S-0 crossing in the strong polar solvent reduces the isomerization efficiency.zh_CN
dc.description.sponsorshipResearch Grants Council of Hong Kong SAR [CityU 103106]; National Science Foundation [20173042, 20473062, 20233020, 20021002]; Ministry of Science and Technology [2004CB719902, 001CB1089]; Ministry of Educationzh_CN
dc.language.isoenzh_CN
dc.publisherWORLD SCIENTIFIC PUBL CO PTE LTDzh_CN
dc.subjectIntramolecular charge transferzh_CN
dc.subjectexcited statezh_CN
dc.subjectpotential surfacezh_CN
dc.subjectphotochemistryzh_CN
dc.subjectcomplete active space self-consistent-fieldzh_CN
dc.titleINTRAMOLECULAR CHARGE TRANSFER AND PHOTOISOMERIZATION OF THE DCM STYRENE DYE: A THEORETICAL STUDYzh_CN
dc.typeArticlezh_CN


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