高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (2): 344-350.doi: 10.7503/cjcu20130863

• 物理化学 • 上一篇    下一篇

气相中HRnCCH和X(X=H2O,NH3)反应机理的理论研究

高成贵1, 隆正文1(), 谭兴凤2, 龙波1,2(), 张为俊3, 龙超云1, 秦水介1   

  1. 1. 贵州大学物理系, 贵阳 550025
    2. 贵州民族大学信息工程学院, 贵阳 550025
    3. 中国科学院安徽光学精密机械研究所环境光谱实验室, 合肥 230031
  • 收稿日期:2013-09-05 出版日期:2014-02-10 发布日期:2013-12-30
  • 作者简介:联系人简介: 隆正文, 男, 教授, 博士生导师, 主要从事大气化学研究. E-mail:sci.zwlong@gzu.edu.cn; 龙 波, 男, 博士, 副教授, 主要从事大气化学研究. E-mail : longbo@gzmu.edu.cn
  • 基金资助:
    国家自然科学基金(批准号: 41165007)、 贵州省科学技术基金(批准号: 黔科合J字[2011]2107, 黔科合J字[2012]2189)、 中国科学院大气成分与光学重点实验室开放课题(批准号: JJ1107)和贵州大学研究生创新基金(批准号: 2013023)资助

Theoretical Investigation on the Reaction Between HRnCCH and X(X=H2O, NH3) in Gas Phase

GAO Chenggui1, LONG Zhengwen1,*(), TAN Xingfeng2, LONG Bo1,2,*(), ZHANG Weijun3, LONG Chaoyun1, QIN Shuijie1   

  1. 1. Department of Physics, Guizhou University, Guiyang 550025, China
    2.College of Information Engineering, Guizhou Minzu University, Guiyang 550025, China
    3.Laboratory of Environment Spectroscopy, Anhui Institute of Optics and Fine Mechanics,Chinese Academy of Sciences, Hefei 230031, China
  • Received:2013-09-05 Online:2014-02-10 Published:2013-12-30
  • Contact: LONG Zhengwen,LONG Bo E-mail:sci.zwlong@gzu.edu.cn;longbo@gzmu.edu.cn
  • Supported by:
    † Supported by the National Natural Science Foundation of China(No.41165007), the Science and Technology Foundation of Guizhou Province, China(Nos.20102107, 20122189), the Open Research Fund of Key Laboratory of Atmospheric Composition and Optical Radiation, Chinese Academy of Sciences(No.JJ1107) and the Graduate Innovation Foundation of Guizhou University, China(No.2013023)

摘要:

在CCSD(T)//MP2/aug-cc-pVTZ-pp理论水平上, 研究了HRnCCH与大气中H2O及NH3分子反应的机理, 反应主要包括HRnCCH与HRnOH及HRnNH2之间的转化、 H2O和NH3在HRnCCH中的碳碳三键上的加成反应以及HRnCCH与双分子水反应等. 结果表明, HRnCCH与H2O反应生成HCCH和HRnOH及HRnCCH与NH3反应生成HCCH和HRnNH2的能垒分别为54.1和75.2 kJ/mol, 而生成HRnCHC(OH)H, HRnC(OH)CH2, HRnCHC(NH2)H和HRnC(NH2)CH2的活化能分别为219.6, 220.5, 174.4和182.4 kJ/mol, 此结果表明HRnCCH反应性较弱且是稳态存在的. 此外, 在HRnCCH与H2O反应中加入单个水分子, 仍然生成HRnCHC(OH)H, 但反应活化能却降低了96.4 kJ/mol, 说明水分子对该反应有明显的催化作用.

关键词: HRnCCH, 量子化学计算, 反应机理, 水, 氨气

Abstract:

The reaction mechanisms of HRnCCH with H2O, NH3 were explored at the CCSD(T)//MP2/aug-cc-pVTZ-pp level of theory. This investigation involved the conversion between HRnCCH and HRnOH, HRnCCH and HRnNH2, and the water, water dimer, and ammonia gas molecule addition to the C≡C bond in the HRnCCH, respectively. The calculated results show that the HCCH+HRnOH is produced by the reaction of HRnCCH+H2O with an activated barrier of 54.1 kJ/mol and HCCH+HRnNH2 is yielded via the reaction of HRnCCH+NH3 with a estimated barrier of 75.2 kJ/mol. However, the formations of HRnCHC(OH)H, HRnC(OH)CH2, HRnCHC(NH2)H and HRnC(NH2)CH2 have the respective barrier of 219.6, 220.5, 174.4 and 182.4 kJ/mol. Therefore, the reactivity of HRnCCH is of quite weakness at the environments investigated herein, which indicates that HRnCCH could be existed under these conditions. In addition, the second water molecule introduced into the HRnCCH+H2O reaction leads to the remarkable reduction for the barrier of the formation of HRnCHC(OH)H to 123.2 kJ/mol, in which the second water molecule plays a strong catalytic role in the reaction of HRnCCH with water.

Key words: HRnCCH, Quantum chemical calculation, Reaction mechanism, Water, Ammonia gas

中图分类号: