Mode-Specific Tunneling Splittings for a Sequential Double-Hydrogen Transfer Case: An Accurate Quantum Mechanical Scheme

	Mode-Specific Tunneling Splittings for a Sequential Double-Hydrogen Transfer Case: An Accurate Quantum Mechanical Scheme
	Ren, Yinghui 1,2; Bian, Wensheng 1
刊名	JOURNAL OF PHYSICAL CHEMISTRY LETTERS
	2015-05-21
卷号	6 期号:10 页码:1824-1829
英文摘要	We present the first accurate quantum dynamics calculations of mode-specific tunneling splittings in a sequential double-hydrogen transfer process. This is achieved in the vinylidene-acetylene system, the simplest molecular system of this kind, and by large-scale parallel computations with an efficient theoretical scheme developed by us. In our scheme, basis functions are customized for the hydrogen transfer process; a 4-dimensional basis contraction strategy is combined with the preconditioned inexact spectral transform method; efficient parallel implementation is achieved. Mode-specific permutation tunneling splittings of vinylidene states are reported and tremendous mode-specific promotion effects are revealed; in particular, the CH2 rock mode enhances the ground-state splitting by a factor of 10(3). We find that the ground-state vinylidene has a reversible-isomerization time of 622 ps, much longer than all previous estimates. Our calculations also shed light on the importance of the deep intermediate well and vibrational excitation in the double-hydrogen transfer processes.
收录类别	SCI
语种	英语
公开日期	2015-11-02
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/28131]
专题	化学研究所_分子反应动力学实验室
作者单位	1.Chinese Acad Sci, Inst Chem, Beijing Natl Lab Mol Sci, Beijing 100190, Peoples R China 2.Univ Chinese Acad Sci, Beijing 100049, Peoples R China
推荐引用方式 GB/T 7714	Ren, Yinghui,Bian, Wensheng. Mode-Specific Tunneling Splittings for a Sequential Double-Hydrogen Transfer Case: An Accurate Quantum Mechanical Scheme[J]. JOURNAL OF PHYSICAL CHEMISTRY LETTERS,2015,6(10):1824-1829.
APA	Ren, Yinghui,&Bian, Wensheng.(2015).Mode-Specific Tunneling Splittings for a Sequential Double-Hydrogen Transfer Case: An Accurate Quantum Mechanical Scheme.JOURNAL OF PHYSICAL CHEMISTRY LETTERS,6(10),1824-1829.
MLA	Ren, Yinghui,et al."Mode-Specific Tunneling Splittings for a Sequential Double-Hydrogen Transfer Case: An Accurate Quantum Mechanical Scheme".JOURNAL OF PHYSICAL CHEMISTRY LETTERS 6.10(2015):1824-1829.