A theoretical treatment of the intersystem crossing in the spin-forbidden reaction N(S-4)+CS2 (X-1 Sigma(+)(g))-> NS(X-2 Pi)+CS(X-1 Sigma(+))

doi:10.1016/j.theochem.2006.03.043

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	A theoretical treatment of the intersystem crossing in the spin-forbidden reaction N(S-4)+CS2 (X-1 Sigma(+)(g))-> NS(X-2 Pi)+CS(X-1 Sigma(+))
	Lu, Ling-Ling ; Wang, Xiao-Fang ; Wang, Yong-Cheng ; Wang, Han-Qin
刊名	JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM
	2006-09-29
卷号	770 期号:1-3 页码:1-6
关键词	n(S-4) And Cs2(x (1)Sigma(+)(g)) Reaction Mechanism Intersystem Crossing
ISSN号	0166-1280
DOI	10.1016/j.theochem.2006.03.043
英文摘要	The mechanism of the spin-forbidden reaction N(S-4) + CS2 (X-1 Sigma(+)(g)) -> NS(X-2 Pi) + CS(X-1 Sigma(+)) on both doublet and quartet potential energy surfaces has been investigated at B3LYP, CCSD(T) and CASSCF levels of theory. The minimum energy point (MEX-1) on the doublet-quartet crossing surface is determined using the complete-active-space-self-consistent field (CASSCF) calculations with (3,4), (5,5), (7,6), and (7,7) active spaces with a weighting of 50%/50% to the doublet and quartet states. The minimum energy point (MEX-1) has a Cs structure resembling the intermediate structure M-2-1. The intersystem crossing at the MEX-1 crossing point is taking place, and it is attributed to the stronger spin-orbit coupling (SOC)(50.2-75.5 cm(-1)) and the barrier (65.01-72.10 kJ/mol) with respect to the ground state reactants N(S-4) + CS2(X-1 Sigma(+)(g)). This is in close agreement with the experimental observation reporting large rate coefficients. (c) 2006 Elsevier B.V. All rights reserved.
语种	英语
出版者	ELSEVIER SCIENCE BV
WOS记录号	WOS:000241243900001
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/58031]
专题	中国科学院化学研究所
通讯作者	Lu, Ling-Ling
作者单位	1.Tianshui Normal Univ, Coll Life Sci & Chem, Tianshui 741001, Gansu, Peoples R China 2.NW Normal Univ, Coll Chem & Chem Engn, Lanzhou 730070, Gansu, Peoples R China 3.Chinese Acad Sci, Inst Chem & Phys, Lanzhou 730070, Gansu, Peoples R China
推荐引用方式 GB/T 7714	Lu, Ling-Ling,Wang, Xiao-Fang,Wang, Yong-Cheng,et al. A theoretical treatment of the intersystem crossing in the spin-forbidden reaction N(S-4)+CS2 (X-1 Sigma(+)(g))-> NS(X-2 Pi)+CS(X-1 Sigma(+))[J]. JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM,2006,770(1-3):1-6.
APA	Lu, Ling-Ling,Wang, Xiao-Fang,Wang, Yong-Cheng,&Wang, Han-Qin.(2006).A theoretical treatment of the intersystem crossing in the spin-forbidden reaction N(S-4)+CS2 (X-1 Sigma(+)(g))-> NS(X-2 Pi)+CS(X-1 Sigma(+)).JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM,770(1-3),1-6.
MLA	Lu, Ling-Ling,et al."A theoretical treatment of the intersystem crossing in the spin-forbidden reaction N(S-4)+CS2 (X-1 Sigma(+)(g))-> NS(X-2 Pi)+CS(X-1 Sigma(+))".JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM 770.1-3(2006):1-6.