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	A theoretical study on photodissociation of the a state of the h2s+ ion
	Chang, Hai-Bo; Huang, Ming-Bao
刊名	Theoretical chemistry accounts
	2009-03-01
卷号	122期号:3-4页码:189-196
关键词	H2s+ ion Caspt2 Photodissociation
ISSN号	1432-881X
通讯作者	Huang, ming-bao(mbhuang1@gucas.ac.cn)
英文摘要	We have studied photodissociation of the a state of the h2s+ ion using the quantum-chemical cas methods, and the 1(2) a '' (x-2 b-1) and 1(4) a '' states are involved in photodissociation of the 1(2) a' (a(2) a(1)) state ( the electronic states in dissociation were studied in the c-s symmetry). the caspt2 s-loss dissociation potential energy curve (pec) calculations indicate that the 1(2) a '' and 1(2) a' states correlate with the second limit [h-2 + s+(d-2)] while the 1(4) a '' state correlates with the first limit [h-2 + s+(s-4)] and that there are a transition state and a local minimum along the 1(2) a' pec and the repulsive 1(4) a '' pec crosses the 1(2) a '' and 1(2) a' pecs. the caspt2 h-loss dissociation pec calculations indicate that the 1(2) a '' and 1(4) a '' states correlate with the first limit [hs+(x-3 sigma(-))+ h] while the 1(2) a' state correlates with the second limit [hs+(a(1) delta) + h] and that the repulsive 1(4) a '' pec crosses the 1(2) a' pec. for the crossing doublet and quartet states in pairs, we performed casscf minimum energy crossing point ( mecp) calculations, and the casscf spin-orbit couplings and caspt2 energies at the mecp geometries were calculated. we examined the two previously proposed mechanisms ( mechanisms i and ii) for dissociation of the a state to the s? ion, based on our calculation results. we suggest processes for dissociation of the a state to the s? ion ( processes i and ii, based on mechanisms i and ii, respectively) and to the sh+ ion ( process iii) and conclude that photodissociation of the a state mainly leads to the s? ion via the most energetically favorable process ii: a(2) a(1) (1(2) a') (2.38 ev) -> barrier at the linearity (2.96 ev) -> x-2 b-1 (1(2) a '') (0.0 ev) -> the 1(2) a ''/1(4) a '' mecp (3.50 ev, large spin-orbit coupling) -> h-2(x-1 sigma(+)(g)) + s+ (s-4) ( 2.92 ev) ( the caspt2 relative energy values to x-2 b-1 are given in parentheses and the largest value is 3.50 ev at the mecp).
WOS关键词	2ND-ORDER PERTURBATION-THEORY ; HE-ASTERISK(2(3)S) PENNING IONIZATION ; MOLECULAR WAVE-FUNCTIONS ; ANO BASIS-SETS ; ELECTRONIC STATES ; HYDROGEN-SULFIDE ; ROW ATOMS ; PHOTOELECTRON ; SPECTROSCOPY ; PHOTOIONIZATION
WOS研究方向	Chemistry
WOS类目	Chemistry, Physical
语种	英语
出版者	SPRINGER
WOS记录号	WOS:000263509400008
内容类型	期刊论文
URI标识	http://www.corc.org.cn/handle/1471x/2397890
专题	中国科学院大学
通讯作者	Huang, Ming-Bao
作者单位	Chinese Acad Sci, Grad Univ, Coll Chem & Chem Engn, Beijing 100049, Peoples R China
推荐引用方式 GB/T 7714	Chang, Hai-Bo,Huang, Ming-Bao. A theoretical study on photodissociation of the a state of the h2s+ ion[J]. Theoretical chemistry accounts,2009,122(3-4):189-196.
APA	Chang, Hai-Bo,&Huang, Ming-Bao.(2009).A theoretical study on photodissociation of the a state of the h2s+ ion.Theoretical chemistry accounts,122(3-4),189-196.
MLA	Chang, Hai-Bo,et al."A theoretical study on photodissociation of the a state of the h2s+ ion".Theoretical chemistry accounts 122.3-4(2009):189-196.

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