FACILITATED PHOTOLYSIS OF 9-FLUORENOL IN ALCOHOLS BY EXCITED-STATE HYDROGEN BOND REORGANIZATION

	FACILITATED PHOTOLYSIS OF 9-FLUORENOL IN ALCOHOLS BY EXCITED-STATE HYDROGEN BOND REORGANIZATION
	Liu, Yu-Hui 1; Zhou, Pan-Wang
刊名	journal of theoretical & computational chemistry
	2012-06-01
卷号	11 期号:3 页码:493-504
关键词	The photolysis dynamics 9-fluorenol time-dependent density functional theory
通讯作者	周潘旺
产权排序	1,1
英文摘要	time-dependent density functional theory (tddft) and second-order coupled cluster method with resolution-of-the-identity approximation (ricc2) were used to investigate the photolysis dynamics of 9-fluorenol (foh) in alcohols. in this work, a novel mechanism for the accelerated photolysis dynamics of foh in alcohols is proposed for the first time. the two hydrogen bonds present different effects in the dissociation process of c-9-o bond in meoh center dot center dot center dot foh center dot center dot center dot meoh trimer: formation of hydrogen bond meoh center dot center dot center dot foh could weaken the c9-o bond, while, hydrogen bond foh center dot center dot center dot meoh fastens the bond. moreover, the thermodynamic equilibrium can be accomplished in both ground and excited states between hydrogen-bonded complexes, since the hydrogen bond reorganization occurs in hundreds of femtosecond upon the excitation. the excited-state potential energy (pe) curves along c9-o bond have been optimized in s-1 state. the cleavage of c9-o bond upon the photoexcitation would be facilitated effectively in meoh center dot center dot center dot foh dimer. this leads the thermodynamic equilibrium between hydrogen-bonded complexes leaning to the side of meoh center dot center dot center dot foh dimer to quench the fluorescence. therefore, the photolysis of 9-fluorenol in alcohols can be facilitated effectively by meoh center dot center dot center dot foh hydrogen bond via excited-state hydrogen bond reorganization. additionally, the excited-state hydrogen bond reorganization is also the rate-controlling step in photolysis of foh in alcohols, since there is no barrier in the pe curve of meoh center dot center dot center dot foh dimer.
学科主题	物理化学
WOS标题词	science & technology ; physical sciences
类目[WOS]	chemistry, multidisciplinary
研究领域[WOS]	chemistry
关键词[WOS]	intramolecular proton-transfer ; aqueous-solution ; photodissociation dynamics ; electronic-structure ; 266 nm ; time ; cation ; photosolvolysis ; fluorescence ; derivatives
收录类别	SCI
语种	英语
WOS记录号	WOS:000305540600002
公开日期	2013-10-11
内容类型	期刊论文
源URL	[http://159.226.238.44/handle/321008/118075]
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, Peoples R China 2.Chinese Acad Sci, Grad Sch, Beijing 100039, Peoples R China
推荐引用方式 GB/T 7714	Liu, Yu-Hui,Zhou, Pan-Wang. FACILITATED PHOTOLYSIS OF 9-FLUORENOL IN ALCOHOLS BY EXCITED-STATE HYDROGEN BOND REORGANIZATION[J]. journal of theoretical & computational chemistry,2012,11(3):493-504.
APA	Liu, Yu-Hui,&Zhou, Pan-Wang.(2012).FACILITATED PHOTOLYSIS OF 9-FLUORENOL IN ALCOHOLS BY EXCITED-STATE HYDROGEN BOND REORGANIZATION.journal of theoretical & computational chemistry,11(3),493-504.
MLA	Liu, Yu-Hui,et al."FACILITATED PHOTOLYSIS OF 9-FLUORENOL IN ALCOHOLS BY EXCITED-STATE HYDROGEN BOND REORGANIZATION".journal of theoretical & computational chemistry 11.3(2012):493-504.