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论文类型：期刊论文

发表时间：2010-02-05

发表刊物：JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY

收录刊物：SCIE

卷号：210

期号：1

页面范围：77-81

ISSN号：1010-6030

关键字：Dihydrogen bond; Infrared spectra; Electronically excited state; Time-dependent density functional theory

摘要：Intermolecular dihydrogen bonding in the electronically excited states of a phenol-diethylmethylsilane (DEMS) complex was Studied theoretically using the time-dependent density functional theory (TDDFT) method. Analysis of the frontier molecular orbitals revealed a locally excited S(1) state for the dihydrogen-bonded phenol-DEMS complex in which only the phenol moiety is electronically excited. The calculated infrared spectrum of the phenol-DEMS complex is quite different from that of previously studied S(1) state of a dihydrogen-bonded phenol-borane-trimethylamine complex. The O-H and Si-H stretching vibrational modes appear as intense, sharp peaks for the S(1) state which are slightly red-shifted compared with those predicted for the ground state. Upon electronic excitation to the S(1) state, the O-H and Si-H bonds involved in the dihydrogen bond O-H center dot center dot center dot H-Si lengthen slightly, while the C-O bond shortens. The calculated H center dot center dot center dot H distance is significantly shorter in the S(1) state than in the ground state. Thus, the intermolecular dihydrogen bond of the phenol-DEMS complex is stronger in the electronically excited state than in the ground state. (C) 2009 Elsevier B.V. All rights reserved.