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题名: Vibronically induced decay paths from the (C)over-tilde(1)B(1)-state of water and its isotopomers
作者: Dixon, Richard N.1;  Oliver, Thomas A. A.1;  Cheng, Lina2;  Cheng, Yuan2;  Yuan, Kaijun2;  Yang, Xueming2
刊名: JOURNAL OF CHEMICAL PHYSICS
发表日期: 2013-03-14
DOI: 10.1063/1.4794158
卷: 138, 期:10
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Physics, Atomic, Molecular & Chemical
研究领域[WOS]: Physics
英文摘要: The 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]
关键词[WOS]: DEPENDENT QUANTUM DYNAMICS ;  DISSOCIATION DYNAMICS ;  121.6 NM ;  PHOTODISSOCIATION ;  H2O ;  PATHWAYS ;  PICTURE
语种: 英语
WOS记录号: WOS:000316543400031
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/137856
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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作者单位: 1.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:
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).
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