【作者】 李东艳； 郭俊江； 徐佳琪； 谈宁馨； 李象远；

【Author】 Dongyan Li;Junjiang Guo;Jiaqi Xu;Ningxin Tan;Xiangyuan Li;College of Chemical Engineering, Sichuan University;College of Chemistry, Sichuan University;

【机构】 四川大学化学工程学院； 四川大学化学学院；

【摘要】 CH₂CH₂OH是C₂H₄和CH₃CH₂OH氧化反应重要中间体,HO₂是低温条件下浓度较大的自由基^[1]。本文通过精确地量子化学计算补充该反应通道并进一步完善低温氧化反应核心机理。采用高精度量子化学组合方法CBS-QB3结合传统过渡态理论（TST）、变分过渡态理论（VTST）和RRKM/ME理论计算CH₂CH₂OH+HO₂反应体系速率常数。在B3LYP/CBSB7水平下对反应物、产物和过渡态做几何优化和频率计算,采用CBS-QB3方法进行能量计算。结果表明CH₃CH₂OH+O₂和HO₂CH₂CH₂OH的产物形成反应是主要的竞争通道,并且在低温条件下反应HO₂CH₂CH₂OH=OCH₂CH₂OH+OH以及OCH₂CH₂OH=CH₂OH+CH₂O具有较强的敏感性。更多还原

【Abstract】 Reaction of CH₂CH₂OH radical with HO₂ is of key importance in C₂H₄ and CH₃CH₂OH combustion at low temperature. In this work, all rates were determined computationally using the CBS-QB3 composite method combined with TST, VTST and RRKM/ME theory. The geometries optimization and the vibrational frequency analysis of reactants, transition states and products were performed at the B3LYP/CBSB7 level, single point energies and the thermodynamic parameters were calculated by using the composite CBS-QB3 method. It indicated that CH₂CH₂OH+HO₂=CH₃CH₂OH+O₂ and CH₂CH₂OH+HO₂=HO₂CH₂CH₂OH are important channels, while HO₂CH₂CH₂OH=OCH₂CH₂OH+OH, OCH₂CH₂OH=CH₂OH+CH₂O are much more sensitivity in low temperature.更多还原