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Vibronically induced decay paths from the (C)over-tilde(1)B(1)-state of water and its isotopomers
Dixon, Richard N.1; Oliver, Thomas A. A.1; Cheng, Lina2; Cheng, Yuan2; Yuan, Kaijun2; Yang, Xueming2
Source PublicationJOURNAL OF CHEMICAL PHYSICS
2013-03-14
DOI10.1063/1.4794158
Volume138Issue:10
Indexed BySCI
SubtypeArticle
WOS HeadingsScience & Technology ; Physical Sciences
WOS SubjectPhysics, Atomic, Molecular & Chemical
WOS Research AreaPhysics
WOS KeywordDEPENDENT QUANTUM DYNAMICS ; DISSOCIATION DYNAMICS ; 121.6 NM ; PHOTODISSOCIATION ; H2O ; PATHWAYS ; PICTURE
AbstractThe photochemistry of the water molecule has revealed a wealth of quantum phenomena, which arise from the involvement of several coupled electronic states with very different potential energy surfaces. Most recently, dissociation from single rotational levels of its (C) over tilde B-1(1) state near 124 nm has been attributed to a vibronically coupled decay via the lower (A) over tilde -state surface, despite a large vertical energy gap of 2.8 eV. Similar conclusions have been reached for subsequent experimental data for D2O. The present paper presents further experimental data for HOD and for both the H+OD(X) and D+OH(X) products. Unlike the cases for H2O and D2O, the vibrational populations for hydroxyl products do not follow a smooth distribution with v(OH/OD). In particular, for OH there is a clear alternation in population for all the strong peaks, with odd v favoured over even v. These experimental data are analysed using new MRCI+Q calculations, which have been used to generate potential surfaces and associated non-adiabatic matrix elements for transition from the adiabatic (C) over tilde -state to lower unbound potential surfaces; and hence, to guide dynamical calculations using time-dependent wavepackets. It is concluded that although there is a minor contribution from the (C) over tilde -> (A) over tilde decay route, the major route follows (C) over tilde -> (1)A(2) -> (A) over tilde. This is mediated through two regions of near degeneracy of the elusive (1)A(2) surface with (C) over tilde for short bonds ca. 0.8 angstrom; and between (1)A(2) and (A) over tilde with long bonds >= 2 angstrom, thereby bridging the vertical energy gap. The striking population alternation for the D+OH(X) products is attributed to dynamic symmetry breaking on the (1)A(2) surface. [http://dx.doi.org/10.1063/1.4794158]
Language英语
WOS IDWOS:000316543400031
Citation statistics
Cited Times:8[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://cas-ir.dicp.ac.cn/handle/321008/137856
Collection中国科学院大连化学物理研究所
Affiliation1.Univ Bristol, Sch Chem, Bristol BS8 1TS, Avon, England
2.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China
Recommended Citation
GB/T 7714
Dixon, Richard N.,Oliver, Thomas A. A.,Cheng, Lina,et al. Vibronically induced decay paths from the (C)over-tilde(1)B(1)-state of water and its isotopomers[J]. JOURNAL OF CHEMICAL PHYSICS,2013,138(10).
APA Dixon, Richard N.,Oliver, Thomas A. A.,Cheng, Lina,Cheng, Yuan,Yuan, Kaijun,&Yang, Xueming.(2013).Vibronically induced decay paths from the (C)over-tilde(1)B(1)-state of water and its isotopomers.JOURNAL OF CHEMICAL PHYSICS,138(10).
MLA Dixon, Richard N.,et al."Vibronically induced decay paths from the (C)over-tilde(1)B(1)-state of water and its isotopomers".JOURNAL OF CHEMICAL PHYSICS 138.10(2013).
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