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论文类型：期刊论文

发表时间：2013-04-01

发表刊物：JOURNAL OF PHYSICAL ORGANIC CHEMISTRY

收录刊物：SCIE、EI、Scopus

卷号：26

期号：4

页面范围：289-294

ISSN号：0894-3230

关键字：excited state; hydrogen bonding dynamics; TDDFT; electronic spectra

摘要：The time-dependent density functional theory (TDDFT) method was performed to investigate the excited-state hydrogen bonding dynamics of 4-amino-1,8-naphthalimide (4ANI) as hydrogen bond acceptor in hydrogen donating methanol (MeOH) solvent. The ground-state geometry optimizations, electronic transition energies and corresponding oscillation strengths of the low-lying electronically excited states for the isolated 4ANi and hydrogen-bonded 4ANi-(MeOH)1,4 complexes were calculated by the DFT and TDDFT methods, respectively. We demonstrated that the intermolecular hydrogen bond CO center dot center dot center dot HO and NH center dot center dot center dot OH in the hydrogen-bonded 4ANi-(MeOH)1,4 is strengthened in the electronically excited state, because the electronic excitation energies of the hydrogen-bonded complex are correspondingly decreased compared with that of the isolated 4ANi. The calculated results are consistent with the mechanism of the hydrogen bond strengthening in the electronically excited state, while contrast with mechanism of hydrogen bond cleavage. Furthermore, we believe that the transient hydrogen bond strengthening behavior in electronically excited state of fluorescent dye in hydrogen-donating solvents exists in many other systems in solution. Copyright (c) 2013 John Wiley & Sons, Ltd.