物理化学学报 >> 1995, Vol. 11 >> Issue (01): 31-37.doi: 10.3866/PKU.WHXB19950107

研究论文 上一篇    下一篇

单次碰撞条件下Ar(3P0.2)与SO2,SOCl2的传能反应

孙琦, 顾月姝, 郭敬忠, 印永嘉, 李学初, 沈关林   

  1. 山东大学化学系|济南 250100|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
  • 收稿日期:1993-10-04 修回日期:1994-03-07 发布日期:1995-01-15
  • 通讯作者: 顾月姝

Energy Transfer Reactions of Ar(3P0.2)与SO2,SOCl2 under the Single Collision Condition

Sun Qi, Gu Yue-Shu, Guo Jing-Zhong, Yin Yong-Jia, Li Xue-Chu, Shen Guan-Lin   

  1. Chemistry Department|Shandong University,Jinan 250100|State Key Laboaratory of Molecular Reaction Dynamics,Dalian Institute of Chemical Physics,CAS,Dalian 116023
  • Received:1993-10-04 Revised:1994-03-07 Published:1995-01-15
  • Contact: Gu Yue-Shu

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摘要：

利用化学发光方法研究了Ar（3P0,2）与SO2，SOCl2在单次碰撞条件下SO（A）的形成动力学，通过对实验光谱进行曲线拟会，得到了SO（A，υ＇）的初生态布居．分别是N0：N1：N2：N3：N4：N5：N6＝1．00：0．67：0．57：0．55：0．50：0．35：0．30和1．00：0．69：0．61：0．53：0．40：0．34：0．26．利用参考反应法求算了SO（A）的形成速率，分别为：4．55×10－12cm3•molecule－1•s－1和2．87×10－12cm3•molecule－1•s－1，与总猝灭速率相比较，发现解离激发为反应的次要出口通道．通过惊奇度分析，对激发解离机理进行了讨论．

关键词: 亚稳态, 解离激发, 振动布居, 反应通道

Abstract:

 Dissociative excitation of SO2,SOCl2 through single collision with Ar(3P0,2)have been studied by observing SO(A - X) emission in the beam apparatus. The nascent vibrational distribution of SO(A, υ＇) was determined. A Surprisal analysis of the nascent vibrational distribution of SO(A) indicated that the precursor molecules dissociation could occur predominately from superexcited states (Rydberg-states). The formation rate constants of SO(A) have been determined for Ar(3P0,2)/SO2 and Ar(3P0,2)/SOCl2 reactions, They are: 4．55×10－12cm3•molecule－1•s－1 and 2．87×10－12cm3•molecule－1•s－1, respectively. A comparison between the observed formation rate constants and known total quenching rate constants indicated that dissociative excitation processes are monitor exit channels.

Key words: Metastable atom, Dissociative excitation, Vibrational distribution, Reaction channel