物理化学学报 >> 1998, Vol. 14 >> Issue (04): 327-331.doi: 10.3866/PKU.WHXB19980408

研究论文 上一篇    下一篇

CO(υ)高振动激发态向C2H2的振动传能研究

王宝山, 郭敬忠, 顾月姝, 毛文涛, 孔繁敖   

  1. 山东大学化学系，济南 250100;中国科学院化学研究所，分子反应动力学国家重点实验室，北京 100080
  • 收稿日期:1997-07-07 修回日期:1997-11-03 发布日期:1998-04-15
  • 通讯作者: 顾月姝

Vibrational Energy Transfer from Highly Excited State CO to C2H2

Wang Bao-Shan, Guo Jing-Zhong, Gu Yue-Shu, Mao Wen-Tao, Kong Fan-Ao   

  1. Department of Chemistry,Shandong University,Jinnan 250100|State Key Laboratory of Molectlar Rection Dynamics,Institute of Chemistry,Chinese Academy of Sciences,Beijing 100080
  • Received:1997-07-07 Revised:1997-11-03 Published:1998-04-15
  • Contact: Gu Yue-Shu

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摘要：

用时间分辨窝里叶红外发射谱研究了高振动激发态CO向C2H2的传能，得到了CO（v＝1－3）各振动态布展及其随时间的变化. 利用微分法解出弛豫微分方程组，获得CO（v=1-3）向C2H2的传能速率常数分别为：2.0±0.1，6.0±0.2和9.1±0.8（10-13cm3•molecule-1•s-1）．传能速率随着振动量子数的增加而迅速增加．CO的振动能应向C2H2的对称伸缩模v2近共振V－V传递．传能过程中还可能形成二聚体络合物，加速了CO（v）向C2H2的传能．用ab initio方法确定了CO...C2H2两种可能的直线构型．

关键词: 时间分辨红外光谱, 高振动激发态, V-V传能

Abstract:

 The energy transfer process of highly vibrational states of CO with C2H2 has been studied by the Time -resolved Fourier Transform Infrared Emission Spectroscopy. The vibrational population of CO(v=1-3)were obtained by the simulations of the IR emission spectra. Differentiation method was used to calculate the quenching rate constants of CO(v=1-3)which are:2.0±0.1，6.0±0.2and 9.4±0.8(10-13cm3.molecule-1.s-1), respectively. The most possible energy transfer channel is the transfer of CO(v)to C2H2(v2). Dimer complexes may be formed in the collisional process. The equilibrium structures and lifetime of the complexes were estimated by ab initio computation and V-V/R theory.

Key words: Time-resolved IR spectra, Highly vibrational excited state, V-V energy transfer