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Excited‐state hydrogen bond strengthening of coumarin 153 in ethanol solvent: a TDDFT study
Author(s) -
Xu Jinmei,
Chen Junsheng,
Dong Shunle,
Fu Aiping,
Li Hongliang,
Chu Tianshu
Publication year - 2016
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.3537
Subject(s) - chemistry , coumarin , time dependent density functional theory , hydrogen bond , ethanol , excited state , solvent effects , photochemistry , solvent , computational chemistry , organic chemistry , density functional theory , molecule , atomic physics , physics
So far, coumarin dyes have been extensively studied with various means to understand their photophysical behaviors and photochemical properties. Here, our performing time‐dependent density functional theory calculation is aimed at exploring the excited‐state hydrogen bonding dynamics of coumarin 153 (C153) in protic ethanol (EtOH) solvent. The calculated results suggest that the excited‐state hydrogen bond CO⋯HO between CO group and OH group in the C153‐EtOH complex is strengthened, and the S 0 → S 1 transition of the complex corresponds to the highest occupied molecular orbital (HOMO) hopping to the lowest unoccupied molecular orbital (LUMO). The excited‐state hydrogen bond strengthening has been further confirmed by its larger binding energy in the S 1 state than in the S 0 state. In addition, because of the formation of the hydrogen bond CO⋯HO, a red shift of about 7 nm occurs in the electronic spectra of the C153‐EtOH complex, which is in good accordance with the experiment result. Copyright © 2016 John Wiley & Sons, Ltd.