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	A theoretical study on the electronic states and o-loss photodissociation of the no2+ ion
	Chang, Hai-Bo; Huang, Ming-Bao
刊名	Chemphyschem
	2009-02-23
卷号	10期号:3页码:582-589
关键词	Ab initio calculations Electronic structure Ions Photochemistry Reaction mechanisms
ISSN号	1439-4235
DOI	10.1002/cphc.200800626
通讯作者	Huang, ming-bao(mbhuang1@gucas.ac.cn)
英文摘要	Caspt2 (multiconfiguration second-order perturbation theory) calculations were performed at the molecular geometry for 17 low-lying singlet and triplet states of the no2+ ion. the caspt2 vertical relative energies (t-v') were obtained and the characters of these ionic states (primary or shake-up ionization states) were determined. for the eight low-lying states, we performed caspt2 geometry optimization calculations and obtained the caspt2 adiabatic relative energies (t-0). we conclude that the 1(1)a(1), 1(3)b(2), 1(3)a(2), 1(1)a(2), 1(1)b(2), 1(3)a(1), 2(3)b(2), and 3(3)b(2) states of no2+ correspond to the x-1 sigma(+)(g), a(3)b(2), b(3)a(2), a(1)a(2), (bb2)-b-1, c(3)a(1), d(3)b(1), and (3b(2))(-1) b-3(2) states (the eight ionic states below 20 ev observed in the photoelectron spectra of brundle etal.([1]) and baltzer et al.([2]), respectively. the 1(1)a(1), 1(3)b(2), 1(3)a(2) 1 (1)a(2), 1 b-1(2), 1(3)a(1), and 3(3)b(2) states are primary ionizotion states, and the caspt2 t-v' and t-0 values of these states are close to the corresponding experimental values from refs. [1] and [2]. the 2 3 b, state is not a typical primary ionization state, and the caspt2 t-v' and t-0 values for 2(3)b(1) are in reasonable agreement with the experimental values for db, from refs. [1] and [2] (the caspt2 t-0 value for 13 b, is more than 2.5 ev smaller than the experimental values). based on our caspt(2) t-0 calculations, we comment on the assignments of the d(3)a(1), (cb1)-b-1, and (db2)-b-1 states below 20 ev observed by jarvis et al. and on the mrci to values of hirst for the 1(3)b(1), 1(1)b(1), and (3)a(1) states. on the basis of the caspt2 potential energy curve (pec) and casscf singlet/triplet minimum-energy crossing point (mecp) calculations, we reach the following conclusions concerning o-loss photodissociation from the x-1 sigma(+)(g), a(3)b(2), b(3)a(2), a(1)a(2), and (bb2)-b-1 states, which are in line with the experimental facts. the adiabatic dissociation process of the x-1 sigma(+)(g) state to the second limit [no+(x-1 sigma(+))+ o(d-1)] cannot occur due to a high energy barrier (> 5.0 ev) along the pec, and the nonadiabitic process of x-1 sigma(+)(g) to the first limit [no+(x-1 sigma(+)) + o(p-3)] via the triplet states is unlikely since the mecps lie very high above x-1 sigma(+)(g). for the a(3)b(2) and b(3)a(2) states, adiabatic dissociation processes to the first limit may occur. both the a(1)a(2) and (bb2)-b-1 states can undergo processes of predissociation to the first limit by a repulsiv 2(3)a '' state, since the mecps lie low above a(1)a(2) and (bb2)-b-1 and the calculated spin-orbit couplings at the mecps are not small.
WOS关键词	MOLECULAR WAVE-FUNCTIONS ; ANO BASIS-SETS ; IMPACT IONIZATION ; NITROGEN-DIOXIDE ; CROSS-SECTIONS ; DISSOCIATIVE PHOTOIONIZATION ; EXCITED NO2+ ; ROW ATOMS ; THRESHOLD ; PHOTOELECTRON
WOS研究方向	Chemistry ; Physics
WOS类目	Chemistry, Physical ; Physics, Atomic, Molecular & Chemical
语种	英语
出版者	WILEY-BLACKWELL
WOS记录号	WOS:000264229900020
内容类型	期刊论文
URI标识	http://www.corc.org.cn/handle/1471x/2395485
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 the electronic states and o-loss photodissociation of the no2+ ion[J]. Chemphyschem,2009,10(3):582-589.
APA	Chang, Hai-Bo,&Huang, Ming-Bao.(2009).A theoretical study on the electronic states and o-loss photodissociation of the no2+ ion.Chemphyschem,10(3),582-589.
MLA	Chang, Hai-Bo,et al."A theoretical study on the electronic states and o-loss photodissociation of the no2+ ion".Chemphyschem 10.3(2009):582-589.

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