Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Renmin Road 5268, Changchun, Jilin 130024, People's Republic of China.
J Comput Chem. 2010 Apr 30;31(6):1126-34. doi: 10.1002/jcc.21397.
The reaction of H radical with C(2)H(5)CN has been studied using various quantum chemistry methods. The geometries were optimized at the B3LYP/6-311+G(d,p) and B3LYP/6-311++G(2d,2p) levels. The single-point energies were calculated using G3 and BMC-CCSD methods based on B3LYP/6-311++G(2d,2p) geometries. Four mechanisms were investigated, namely, hydrogen abstraction, C-addition/elimination, N-addition/elimination and substitution. The kinetics of this reaction were studied using the transition state theory and multichannel Rice-Ramsperger-Kassel-Marcus methodologies over a wide temperature range of 200-3000 K. The calculated results indicate that C-addition/elimination channel is the most feasible over the whole temperature range. The deactivation of initial adduct C(2)H(5)CHN is dominant at lower temperature with bath gas H(2) of 760 Torr; whereas C(2)H(5)+HCN is the dominant product at higher temperature. Our calculated rate constants are in good agreement with the available experimental data.
使用各种量子化学方法研究了 H 自由基与 C(2)H(5)CN 的反应。在 B3LYP/6-311+G(d,p) 和 B3LYP/6-311++G(2d,2p) 水平上优化了几何形状。单点能使用 G3 和 BMC-CCSD 方法基于 B3LYP/6-311++G(2d,2p) 几何结构进行计算。研究了四种机制，即氢提取、C 添加/消除、N 添加/消除和取代。使用过渡态理论和多通道 Rice-Ramsperger-Kassel-Marcus 方法在 200-3000 K 的宽温度范围内研究了该反应的动力学。计算结果表明，在整个温度范围内，C 添加/消除通道是最可行的。在较低温度下，初始加合物 C(2)H(5)CHN 以与 760 托的氢气的失活为主；而在较高温度下，C(2)H(5)+HCN 是主要产物。我们计算的速率常数与现有的实验数据吻合较好。
