高等学校化学学报 ›› 1994, Vol. 15 ›› Issue (10): 1529.

• 论文 • 上一篇    下一篇

He(23s)与CHnCl4-n(n=1~4)在束-气条件下的传能解离激发反应

李全新1, 赖热1, 陈从香1, 马兴孝1, 李学初2, 沈关林2   

  1. 1. 中国科学技术大学化学物理系, 合肥, 230026;
    2. 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
  • 收稿日期:1993-11-26 修回日期:1994-06-05 出版日期:1994-10-24 发布日期:1994-10-24
  • 通讯作者: 马兴孝.
  • 作者简介:李全新,男,30岁,博士,讲师.
  • 基金资助:

    国家重点实验室资助

Dissociation Excitation of CHnCl4-n(n=1-4)by the Energy Transfer of He(23 s)Under a Beam-Gas Condition

LI Quan-Xin1, LAI Re1, CHEN Cong-Xiang1, MA Xiang-Xiao1, LI Xue-Chu2, SHEN Guan-Lin2   

  1. 1. Department of Chemical Physics, University of Science and Technology of China, Hefei, 230026;
    2. State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of C'kemical Pkysics. Chinese Academy of Sciences. Dalian, 116023
  • Received:1993-11-26 Revised:1994-06-05 Online:1994-10-24 Published:1994-10-24

摘要: 在束-气条件下,通过检测反应产物的化学发光光谱,研究了亚稳态He(23s)原子与甲烷、氯代甲烷(CHnCl4-n,n=1~3)反应中的解离激发动力学过程。观察到反应的主要激发态碎片CH(A2Δ)、CH(B2Σ-)、CH(C2Σ+)、H和CCl(A2Δ),用参比反应测定了发光碎片的形成速率常数。对CH(A,B)光谱的计算机模拟获得了CH(A2Δ,v′=0~2)和CH(B,v′=0)的振转分布。该反应的可资用能绝大部分转移成产物的平动能,且He(23s)与甲烷及氯代甲烷反应形成CH(A2Δ,v′=0)的转动分布不同,前者为单Boltzmann分布,后者则在低转动能级上转动温度比高转动态低,近似可用双Boltzmann分布描述,对上述反应机理进行了讨论。

关键词: 解离激发, 形成速率常数, 振转分布

Abstract: The kinetic processes of dissociation excitation of CHnCl4-n(n=1-4)colliding with He(23s)were studied by observing the emissions of products。The formation rate constants of CH(A), CH(B), CH(C), Hand CCI(A)from He(23s)/CHnCl4-n(n=1-4)reaction were determined by using the reference reaction method.The rovibrational distribution of CH(A2Δ, v′=0-2)and CH(B2Σ, v′=0)was also obtained by a computer simulation of CH(A-X, B-X)emission. The experimental results showed that the rotational distribution of CH(A2Δ, v′=0)from He(23s)and CHnCl4-n(n=1-3)was expressed as the double Boltzmann temperature, which is different from that of He(23s)/CH4.It is also noted that the major available energies of the reactions are deposited into relative translational energy of products.The mechanism of the reactions He(23s)with CHnCl4-nhas been suggested.

Key words: Dissociation excitation, Formation rate constant, Rovibrational distribution

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