Time-dependent density functional theory study on hydrogen-bonded intramolecular charge-transfer excited state of 4-dimethylamino-benzonitrile in methanol

	Time-dependent density functional theory study on hydrogen-bonded intramolecular charge-transfer excited state of 4-dimethylamino-benzonitrile in methanol
	Zhao, Guang-Jiu 1,2; Han, Ke-Li 1
刊名	journal of computational chemistry
	2008-09-01
卷号	29 期号:12 页码:2010-2017
关键词	hydrogen bond intramolecular charge transfer TDDFT time-resolved infrared spectra excited state internal conversion
通讯作者	韩克利
产权排序	1;1
英文摘要	the time-dependent density functional theory (tddft) method was carried out to investigate the hydrogen-bonded intramolecular charge-transfer (ict) excited state of 4-dimethylaminobenzonitrile (dmabn) in methanol (meoh) solvent. we demonstrated that the intermolecular hydrogen bond c n center dot center dot center dot h-o formed between dmabn and meoh can induce the c n stretching mode shift to the blue in both the ground state and the twisted intramolecular charge-transfer (tict) state of dmabn. therefore, the two components at 2091 and 2109 cm(-1) observed in the time-resolved infrared (trir) absorption spectra of dmabn in meoh solvent were reassigned in this work. the hydrogen-bonded tict state should correspond to the blue-side component at 2109 cm(-1) whereas not the red-side component at 2091 cm(-1) designated in the previous study. it was also demonstrated that the intermolecular hydrogen bond c n center dot center dot center dot h-o is significantly strengthened in the tict state. the intermolecular hydrogen bond strengthening in the tict state can facilitate the deactivation of the excited state via internal conversion (ic), and thus account for the fluorescence quenching of dmabn in protic solvents. furthermore, the dynamic equilibrium of these electronically excited states is explained by the hydrogen bond strengthening in the tict state. (c) 2008 wiley periodicals, inc.
WOS标题词	science & technology ; physical sciences
类目[WOS]	chemistry, multidisciplinary
研究领域[WOS]	chemistry
关键词[WOS]	heptamethine cyanine dye ; resolved resonance raman ; donor-acceptor systems ; ab-initio calculations ; electron-transfer ; bonding nature ; 4-dimethylaminobenzonitrile dmabn ; vibrational spectroscopy ; transient absorption ; molecular-mechanism
收录类别	SCI
原文出处	true
语种	英语
WOS记录号	WOS:000258015500015
公开日期	2010-11-30
内容类型	期刊论文
源URL	[http://159.226.238.44/handle/321008/101175]
专题	大连化学物理研究所_中国科学院大连化学物理研究所
作者单位	1.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Liaoning, Peoples R China 2.Chinese Acad Sci, Grad Sch, Beijing 100049, Peoples R China
推荐引用方式 GB/T 7714	Zhao, Guang-Jiu,Han, Ke-Li. Time-dependent density functional theory study on hydrogen-bonded intramolecular charge-transfer excited state of 4-dimethylamino-benzonitrile in methanol[J]. journal of computational chemistry,2008,29(12):2010-2017.
APA	Zhao, Guang-Jiu,&Han, Ke-Li.(2008).Time-dependent density functional theory study on hydrogen-bonded intramolecular charge-transfer excited state of 4-dimethylamino-benzonitrile in methanol.journal of computational chemistry,29(12),2010-2017.
MLA	Zhao, Guang-Jiu,et al."Time-dependent density functional theory study on hydrogen-bonded intramolecular charge-transfer excited state of 4-dimethylamino-benzonitrile in methanol".journal of computational chemistry 29.12(2008):2010-2017.