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论文类型：期刊论文

发表时间：2011-06-20

发表刊物：Journal of the Korean Chemical Society

收录刊物：EI、Scopus

卷号：55

期号：3

页面范围：385-391

ISSN号：10172548

摘要：The time-dependent density functional theory (TDDFT) method has been carried out to investigate the excitedstate hydrogen-bonding dynamics of phenol-(H2O)2 complex. The geometric structures and infrared (IR) spectra in ground state and different electronically excited states (S1 and T1) of the hydrogen-bonded complex have been calculated using the density functional theory (DFT) and TDDFT method. A ring of three hydrogen bonds is formed between phenol and two water molecules. We have demonstrated that the intermolecular hydrogen bond O1-H 2?O3-H of the three hydrogen bonds is strengthened in S1 and T1 states. In contrast, the hydrogen bond O 5-H6?O1-H is weakened in S1 and T1 states. These results are obtained by theoretically monitoring the changes of the bond lengths of the hydrogen bonds and hydrogen-bonding groups in different electronic states. The hydrogen bond O1-H 2?O3-H strengthening in both the S1 and T1 states is confirmed by the calculated stretching vibrational mode of O-H (phenol) being red-shifted upon photoexcitation. The hydrogen bond strengthening and weakening behavior in electronically excited states may exist in other ring structures of phenol-(H2O)n.