高等学校化学学报Issue(2)：344-350,7.DOI:10.7503/cjcu20130863
气相中HRnCCH和X（X=H2 O,NH3）反应机理的理论研究
Theoretical Investigation on the Reaction Between HRnCCH and X(X=H2 O, NH3) in Gas Phase
摘要
Abstract
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Key words
HRnCCH/Quantum chemical calculation/Reaction mechanism/Water/Ammonia gas分类
化学化工引用本文复制引用
高成贵,隆正文,谭兴凤,龙波,张为俊,龙超云,秦水介..气相中HRnCCH和X（X=H2 O,NH3）反应机理的理论研究[J].高等学校化学学报,2014,(2):344-350,7.基金项目
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.@@@@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) （批准号:41165007）
