title: Reaction dynamics. Extremely short-lived reaction resonances in Cl + HD (v = 1) → DCl + H due to chemical bond softening.
abstract: The Cl + H2 reaction is an important benchmark system in the study of chemical reaction dynamics that has always appeared to proceed via a direct abstraction mechanism, with no clear signature of reaction resonances. Here we report a high-resolution crossed-molecular beam study on the Cl + HD (v = 1, j = 0) → DCl + H reaction (where v is the vibrational quantum number and j is the rotational quantum number). Very few forward scattered products were observed. However, two distinctive peaks at collision energies of 2.4 and 4.3 kilocalories per mole for the DCl (v' = 1) product were detected in the backward scattering direction. Detailed quantum dynamics calculations on a highly accurate potential energy surface suggested that these features originate from two very short-lived dynamical resonances trapped in the peculiar H-DCl (v' = 2) vibrational adiabatic potential wells that result from chemical bond softening. We anticipate that dynamical resonances trapped in such wells exist in many reactions involving vibrationally excited molecules.
authors.affiliation: State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023, China. School of Physics and Optoelectric Engineering, Dalian University of Technology, Dalian, Liaoning 116023, China.
authors.forename: Tiangang
authors.initials: T
authors.lastname: Yang
authors.affiliation: State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023, China.
authors.forename: Jun
authors.initials: J
authors.lastname: Chen
authors.affiliation: State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023, China.
authors.forename: Long
authors.initials: L
authors.lastname: Huang
authors.affiliation: State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023, China.
authors.forename: Tao
authors.initials: T
authors.lastname: Wang
authors.affiliation: State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023, China. chunleixiao@dicp.ac.cn zsun@dicp.ac.cn xmyang@dicp.ac.cn zhangdh@dicp.ac.cn.
authors.forename: Chunlei
authors.initials: C
authors.lastname: Xiao
authors.affiliation: State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023, China. Center for Advanced Chemical Physics and 2011 Frontier Center for Quantum Science and Technology, University of Science and Technology of China, 96 Jinzhai Road, Hefei 230026, China. chunleixiao@dicp.ac.cn zsun@dicp.ac.cn xmyang@dicp.ac.cn zhangdh@dicp.ac.cn.
authors.forename: Zhigang
authors.initials: Z
authors.lastname: Sun
authors.affiliation: State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023, China.
authors.forename: Dongxu
authors.initials: D
authors.lastname: Dai
authors.affiliation: State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023, China. Center for Advanced Chemical Physics and 2011 Frontier Center for Quantum Science and Technology, University of Science and Technology of China, 96 Jinzhai Road, Hefei 230026, China. chunleixiao@dicp.ac.cn zsun@dicp.ac.cn xmyang@dicp.ac.cn zhangdh@dicp.ac.cn.
authors.forename: Xueming
authors.initials: X
authors.lastname: Yang
authors.affiliation: State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023, China. Center for Advanced Chemical Physics and 2011 Frontier Center for Quantum Science and Technology, University of Science and Technology of China, 96 Jinzhai Road, Hefei 230026, China. chunleixiao@dicp.ac.cn zsun@dicp.ac.cn xmyang@dicp.ac.cn zhangdh@dicp.ac.cn.
authors.forename: Dong H
authors.initials: DH
authors.lastname: Zhang