高等学校化学学报

高等学校化学学报 ›› 2002, Vol. 23 ›› Issue (7): 1339.

• 研究论文 • 上一篇    下一篇

不同振动态的CCl2(A1B1)被醇和酮猝灭的动力学

高义德, 陈, 杨学良, 陈从香   

  1. 中国科学院选键化学开放实验室, 中国科学技术大学化学物理系, 合肥 230026
  • 收稿日期:2001-07-03 出版日期:2002-07-24 发布日期:2002-07-24
  • 通讯作者: 陈从香(1941年出生),男,教授,博士生导师,从事激光光谱和分子反应动力学研究.E-mail:cxchen@ustc.edu.cn E-mail:cxchen@ustc.edu.cn
  • 基金资助:

    国家自然科学基金重点项目(批准号:10032050);国家自然科学基金(批准号:29973038);国家重点基础研究专项基金(批准号:G1999075304)资助

The Collisional Quenching of CCl2(A1B1) in Different Vibrational States by Alcohols and Ketones

GAO Yi-De, CHEN Yang, Yang-Xue-Liang, CHEN Cong-Xiang   

  1. Open Laboratory of Bond Selective Chemistry, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China
  • Received:2001-07-03 Online:2002-07-24 Published:2002-07-24

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摘要： 对CCl4/Ar进行混合气体直流脉冲放电产生CCl2自由基,再分别用550.56,541.52,532.25,524.31,523.82和523.27nm激光将电子基态CCl2激励到激发态A1B1的(0,3,0),(0,4,0),(1,3,0),(0,6,0),(1,4,0)和(2,2,0)振动态,通过检测激发态A1B1 CCl2的不同振动态的时间分辨荧光信号(呈双指数衰减),测得室温下A1B1 CCl2的不同振动态被醇类和酮类分子猝灭的实验结果,用三能级模型分析处理实验数据,获得态分辨速率常数kA和ka值.结果表明,其速率常数与振动态的关系并不明显.

关键词: CCl2(A1B1, a3B1)自由基, 动力学, 猝灭速率常数, 三能级模型

Abstract: CCl2 free radicals were produced by dc discharge of CCl4(in Ar). Ground electronic state CCl2 radical was electronically excited to A1B1(0, 3, 0), (0, 4, 0), (1, 3, 0), (0, 6, 0), (1, 4, 0) and (2, 2, 0) vibronic states by Nd∶YAGlaser pumped dye laser at 550.56, 541.52, 532.25, 524.31, 523.82 and 523.37 nm respectively. The experimental quenching data of CCl2( A1B1and a3B1) by alcohols and ketones were obtained by observing time resolved fluorescence from the excited CCl2 radicals transition, which showed a superposition of two exponential decay components. The state-resolved rate constants kA and ka were acquired by analyzing and dealing with these data by using three-level model, which was put forward by us. It is found that the quenching rate constant is not dependent on the vibrational state.

Key words: CCl2( A1B1, a3B1), Kinetics, Quenching rate constant, Three level model

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