Dynamical importance of van der Waals saddle and excited potential surface in C(D-1) + D-2 complex-forming reaction

	Dynamical importance of van der Waals saddle and excited potential surface in C(D-1) + D-2 complex-forming reaction
	Shen, Zhitao 1,2; Ma, Haitao 1; Zhang, Chunfang 1,2; Fu, Mingkai 1,2; Wu, Yanan 1,2; Bian, Wensheng 1,2; Cao, Jianwei 1
刊名	NATURE COMMUNICATIONS
	2017-01-17
卷号	8
英文摘要	Encouraged by recent advances in revealing significant effects of van der Waals wells on reaction dynamics, many people assume that van der Waals wells are inevitable in chemical reactions. Here we find that the weak long-range forces cause van der Waals saddles in the prototypical C(D-1) + D-2 complex-forming reaction that have very different dynamical effects from van der Waals wells at low collision energies. Accurate quantum dynamics calculations on our highly accurate ab initio potential energy surfaces with van der Waals saddles yield cross-sections in close agreement with crossed-beam experiments, whereas the same calculations on an earlier surface with van der Waals wells produce much smaller cross-sections at low energies. Further trajectory calculations reveal that the van der Waals saddle leads to a torsion then sideways insertion reaction mechanism, whereas the well suppresses reactivity. Quantum diffraction oscillations and sharp resonances are also predicted based on our ground- and excited-state potential energy surfaces.
语种	英语
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/38050]
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, Beijing Natl Lab Mol Sci, Inst Chem, State Key Lab Mol React Dynam, Beijing 100190, Peoples R China 2.Univ Chinese Acad Sci, Sch Chem & Chem Engn, Beijing 100049, Peoples R China
推荐引用方式 GB/T 7714	Shen, Zhitao,Ma, Haitao,Zhang, Chunfang,et al. Dynamical importance of van der Waals saddle and excited potential surface in C(D-1) + D-2 complex-forming reaction[J]. NATURE COMMUNICATIONS,2017,8.
APA	Shen, Zhitao.,Ma, Haitao.,Zhang, Chunfang.,Fu, Mingkai.,Wu, Yanan.,...&Cao, Jianwei.(2017).Dynamical importance of van der Waals saddle and excited potential surface in C(D-1) + D-2 complex-forming reaction.NATURE COMMUNICATIONS,8.
MLA	Shen, Zhitao,et al."Dynamical importance of van der Waals saddle and excited potential surface in C(D-1) + D-2 complex-forming reaction".NATURE COMMUNICATIONS 8(2017).