Crossed Beam Experiment on the Validity of Born-Oppenheimer Approximation in Cl(2P)+D2→DCl+D Reaction  

Cl(2P)+D2→DCl+D反应中波恩-奥本海默近似有效性的交叉分子束研究

作　　者：Yu-run Xie Yu-feng Wang Wei Wang Tao Wang Dong-xu Dai Chun-lei Xiao Xue-ming Yang 谢雨润;王玉奉;王威;汪涛;戴东旭;肖春雷;杨学明(中国科学院上海高等研究院,上海201210;中国科学院大连化学物理研究所,分子反应动力学国家重点实验室,大连116023;上海科技大学物质科学与技术学院,上海201210;中国科学院大学,北京100049;南方科技大学理学院,深圳518055)

机构地区：[1]Shanghai Advanced Research Institute,Chinese Academy of Sciences,Shanghai 201210,China [2]State Key Laboratory of Molecular Reaction Dynamics,Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian 116023,China [3]School of Physical Science&Technology,ShanghaiTech University,Shanghai 201210,China [4]University of Chinese Academy of Sciences,Beijing 100049,China [5]College of Science,Southern University of Science and Technology,Shenzhen 518055,China

出　　处：《Chinese Journal of Chemical Physics》2020年第2期135-138,I0002,共5页化学物理学报（英文）

基　　金：supported by the Strategic Priority Research Program of Chinese Academy of Sciences (No.XDB17000000);the National Natural Science Foundation of China (No.21573226,No.21822305,No.21688102).

摘　　要：The reaction of chlorine atom Cl(2P)(Cl(2P3/2)and Cl^*(2P1/2))with D2 was investigated at collision energy from 4.5 kcal/mol to 6.5 kcal/mol with a high-resolution crossed molecular beam apparatus using the technique of D-atom Rydberg tagging detection.The contribution from the spin-orbit excited reaction Cl^*(2P1/2)+D2,which is prohibited by Born-Oppenheimer(BO)approximation,was observed.Collision-energy dependence of differential cross sections(DCSs)near the backward scattering direction was measured.The BOforbidden reaction Cl^*+D2 was found to be dominant at lower collision energy.As collision energy increases,reactivity of BO-allowed reaction Cl+D2 increases much faster than that of BO-forbidden reaction and becomes dominant at higher collision energy.Our experiment indicates that the additional energy of spin-orbit excitation in Cl^*facilitates BO-forbidden reaction to pass through the barrier at lower collision energy,while BO approximation is still valid at collision energy near and above the reaction barrier.This tendency of reactivity of Cl/Cl^*+D2 is similar to the isotopic reaction of Cl/Cl^*+H2.

关 键 词：Spin-orbit state Born-Oppenheimer approximation Crossed beam experiment 

分 类 号：O641.122[理学—物理化学]