New Implementation of Semi-classical Dynamic Simulation on the Photoisomerization of cis- and trans-Isomers of Free Stilbene

doi:10.6023/A12040139

	New Implementation of Semi-classical Dynamic Simulation on the Photoisomerization of cis- and trans-Isomers of Free Stilbene
	Lei Yibo 1,2; Zhu Chaoyuan 2; Wen Zhenyi 1,2; Lin Sheng-Hsien 2
刊名	ACTA CHIMICA SINICA
	2012-09-14
卷号	70 页码:1869-1876
关键词	New Implementation Of Semi-classical Dynamic Simulation Constrained Hamiltonian System Zhu-nakamura Theory Isomerization Of Cis And Trans-stilbene Two Dimensional Analytical Potential Energy Surfaces
ISSN号	0567-7351
DOI	10.6023/A12040139
文献子类	Article
英文摘要	New implementation of semi-classical trajectory surface hopping dynamic simulation has been developed and applied to the photoisomerization of cis- and trans- isomers on the gas phase. This method not only uses the exponential model to the modification of the originally analytical non-adiabatic transition probability formula, but also involves the constrained Hamiltonian system into the constrained molecular dynamic simulation. Two-dimensional potential energy surfaces of ground So and excited SI states are constructed analytically fitting to ab initio calculations in terms of torsion angle and one dihedral angle around the central ethylenic C=C bond as variables, and the other internal coordinates are all fixed at configuration of one-bond flip conical intersection. The analytical PESs are quite accurate and the mean absolute error is less than 2.4 kcal.mol(-1), and much less than 1.0 kcal.mol(-1) around conical intersection region. A straight seam line is found on potential energy surfaces that simply separates the cis-area with the trans-area. The constrained Hamiltonian system is employed to run trajectories in the Cartesian coordinate system and surface hopping in terms of the two internal dihedral angles. Typical trajectories are found in which the torsion angle changes monotonically for both cis- to trans- and trans- to cis-isomerizations. This is an exact picture of one-bond flip mechanism of photoisomerization around the conical intersection. Quantum yield for trans- to cis- isomerization is simulated as 60.45% in very good agreement with experimental value 55.0%, while quantum yield for cis- to trans- isomerization is simulated as 42.3% in comparison with experimental value 35.0%. As the S, energy in local minimum of cis-area is higher than that in trans-area, and thus cis- to trans- isomerization is quite possible to access to another Hula-Twist conical intersection. These simulation results demonstrate that the computed cumulative quantum yield and reaction mechanism are consistent with the previously experimental and theoretical results. This means that the present trajectory surface hopping method would be good at the dynamic simulation on the large system with or without constraint Hamiltonian in comparison with the quantum molecular dynamics.
WOS关键词	CURVE CROSSING PROBLEMS ; SURFACE HOPPING METHOD ; ZHU-NAKAMURA THEORY ; TRANS PHOTOISOMERIZATION ; MOLECULAR-DYNAMICS ; NONADIABATIC TRANSITION ; TEMPERATURE DEPENDENCE ; PHOTOCHEMICAL-REACTION ; HULA-TWIST ; AB-INITIO
语种	英语
出版者	SCIENCE PRESS
WOS记录号	WOS:000309693000017
内容类型	期刊论文
源URL	[http://119.78.100.186/handle/113462/48999]
专题	中国科学院近代物理研究所
通讯作者	Lei Yibo
作者单位	1.NW Univ Xian, Key Lab Synthet & Nat Funct Mol Chem, Minist Educ, Coll Chem & Mat Sci,Shaanxi Key Lab Physicoinorga, Xian 710069, Peoples R China 2.NW Univ Xian, Inst Modern Phys, Xian 710069, Peoples R China
推荐引用方式 GB/T 7714	Lei Yibo,Zhu Chaoyuan,Wen Zhenyi,et al. New Implementation of Semi-classical Dynamic Simulation on the Photoisomerization of cis- and trans-Isomers of Free Stilbene[J]. ACTA CHIMICA SINICA,2012,70:1869-1876.
APA	Lei Yibo,Zhu Chaoyuan,Wen Zhenyi,&Lin Sheng-Hsien.(2012).New Implementation of Semi-classical Dynamic Simulation on the Photoisomerization of cis- and trans-Isomers of Free Stilbene.ACTA CHIMICA SINICA,70,1869-1876.
MLA	Lei Yibo,et al."New Implementation of Semi-classical Dynamic Simulation on the Photoisomerization of cis- and trans-Isomers of Free Stilbene".ACTA CHIMICA SINICA 70(2012):1869-1876.