Theoretical Study of the Reaction of CH3 with HOCO Radicals

被引：16
|
作者：
Yu, Hua-Gen [2 ]
Francisco, Joseph S. [1 ]
机构：
[1] Purdue Univ, Dept Chem, W Lafayette, IN 47907 USA
[2] Brookhaven Natl Lab, Dept Chem, Upton, NY 11973 USA
来源：
JOURNAL OF PHYSICAL CHEMISTRY A | 2009年 / 113卷 / 16期
关键词：
POTENTIAL-ENERGY SURFACE; INITIO QUANTUM SCATTERING; COUPLED-CLUSTER METHODS; AB-INITIO; RATE CONSTANTS; TEMPERATURE-DEPENDENCE; HIGH-PRESSURE; BASIS-SETS; KINETICS; OH;
D O I：
10.1021/jp809730j
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
The reaction of HOCO radicals with CH3 radicals is examined using the coupled cluster method to locate and optimize the critical points on the ground-state potential energy surface. The results show that the CH3 + HOCO reaction can produce both the H2O + CH2CO and the CH4 + CO2 products through acetic acid and enediol intermediates. Direct ab initio dynamics calculations determine the thermal rate coefficients to be k(T/K) = 3.24 x 10(-11)T(0.1024) in cm(3).molec(-1).s(-1) at T <= 1000 K for the overall reaction. In addition, the product branching ratio of (H2O + CH2CO) to (CH4 + CO2) is predicted to be R-H2O/CH4(T/K) = 1.52 + (1.95 X 10(-4))T using RRKM theory. Both the thermal rate coefficients and the product branching ratios are weakly temperature dependent.
引用
收藏
页码：3844 / 3849
页数：6
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