气相中HRnCCH和X(X=H_2O,NH_3)反应机理的理论研究  

Theoretical Investigation on the Reaction Between HRnCCH and X(X= H_2O,NH_3) in Gas Phase

作　　者：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] 

机构地区：[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

出　　处：《高等学校化学学报》2014年第2期344-350,共7页Chemical Journal of Chinese Universities

基　　金：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);贵州大学研究生创新基金(批准号:2013023)资助~~

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182.4kJ/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.The reaction mechanisms of HRnCCH with H2 O, 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＋H2 O 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 in-vestigated herein, which indicates that HRnCCH could be existed under these conditions. In addition, the second water molecule introduced into the HRnCCH＋H2 O 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.

关 键 词：HRnCCH 量子化学计算 反应机理 水 氨气 

分 类 号：O641[理学—物理化学]