Tracking the energy flow in the hydrogen exchange reaction OH + H2O -&gt; H2O + OH

doi:10.1039/c8cp00938d

CORC > 武汉物理与数学研究所 > 中国科学院武汉物理与数学研究所 > 理论与交叉研究部

	Tracking the energy flow in the hydrogen exchange reaction OH + H2O -> H2O + OH
	Bai, Mengna 4; Liu, Yang 4; Yang, Minghui 2; Li, Jun 4; Song, Hongwei 2; Zhu, Yongfa 1,2; Ping, Leilei 2,3
刊名	PHYSICAL CHEMISTRY CHEMICAL PHYSICS
	2018-05-14
卷号	20 期号:18 页码:12543-12556
DOI	10.1039/c8cp00938d
文献子类	Article
英文摘要	The prototypical hydrogen exchange reaction OH + H2O -> H2O + OH has attracted considerable interest due to its importance in a wide range of chemically active environments. In this work, an accurate global potential energy surface (PES) for the ground electronic state was developed based on B44 000 ab initio points at the level of UCCSD(T)-F12a/aug-cc-pVTZ. The PES was fitted using the fundamental invariant-neural network method with a root mean squared error of 4.37 meV. The mode specific dynamics was then studied by the quasi-classical trajectory method on the PES. Furthermore, the normal mode analysis approach was employed to calculate the final vibrational state distribution of the product H2O, in which a new scheme to acquire the Cartesian coordinates and momenta of each atom in the product molecule from the trajectories was proposed. It was found that, on one hand, excitation of either the symmetric stretching mode or the asymmetric stretching mode of the reactant H2O promotes the reaction more than the translational energy, which can be rationalized by the sudden vector projection model. On the other hand, the relatively higher efficacy of exciting the symmetric stretching mode than that of the asymmetric stretching mode is caused by the prevalence of the indirect mechanism at low collision energies and the stripping mechanism at high collision energies. In addition, the initial collision energy turns ineffectively into the vibrational energy of the products H2O and OH while a fraction of the energy transforms into the rotational energy of the product H2O. Fundamental excitation of the stretching modes of H2O results in the product H2O having the highest population in the fundamental state of the asymmetric stretching mode, followed by the ground state and the fundamental state of the symmetric stretching mode.
WOS关键词	ORBITAL ANGULAR-MOMENTUM ; H2O-HO RADICAL COMPLEX ; AB-INITIO ; BIMOLECULAR REACTIONS ; TRANSITION-STATE ; MODE SPECIFICITY ; GAS-PHASE ; SEMICLASSICAL EIGENVALUES ; MICROWAVE-SPECTRUM ; REACTION DYNAMICS
WOS研究方向	Chemistry ; Physics
语种	英语
WOS记录号	WOS:000431825300022
资助机构	National Natural Science Foundation of China(21603266 ; National Natural Science Foundation of China(21603266 ; 21773297 ; 21773297 ; 21573027) ; 21573027) ; National Natural Science Foundation of China(21603266 ; National Natural Science Foundation of China(21603266 ; 21773297 ; 21773297 ; 21573027) ; 21573027)
内容类型	期刊论文
源URL	[http://ir.wipm.ac.cn/handle/112942/12062]
专题	武汉物理与数学研究所_理论与交叉研究部
作者单位	1.Univ Chinese Acad Sci, Beijing 100049, Peoples R China 2.Chinese Acad Sci, Wuhan Inst Phys & Math, State Key Lab Magnet Resonance & Atom & Mol Phys, Wuhan 430071, Hubei, Peoples R China 3.Huazhong Normal Univ, Coll Phys Sci & Technol, Wuhan 430079, Hubei, Peoples R China 4.Chongqing Univ, Sch Chem & Chem Engn, Chongqing 401331, Peoples R China
推荐引用方式 GB/T 7714	Bai, Mengna,Liu, Yang,Yang, Minghui,et al. Tracking the energy flow in the hydrogen exchange reaction OH + H2O -> H2O + OH[J]. PHYSICAL CHEMISTRY CHEMICAL PHYSICS,2018,20(18):12543-12556.
APA	Bai, Mengna.,Liu, Yang.,Yang, Minghui.,Li, Jun.,Song, Hongwei.,...&Ping, Leilei.(2018).Tracking the energy flow in the hydrogen exchange reaction OH + H2O -> H2O + OH.PHYSICAL CHEMISTRY CHEMICAL PHYSICS,20(18),12543-12556.
MLA	Bai, Mengna,et al."Tracking the energy flow in the hydrogen exchange reaction OH + H2O -> H2O + OH".PHYSICAL CHEMISTRY CHEMICAL PHYSICS 20.18(2018):12543-12556.