HCCO与CH(~2Π)双自由基反应微观动力学的理论研究  

Dynamics of Biradical Micro-reaction Between HCCO and CH(~2Π)

作　　者：刘朋军[1] 常鹰飞[2] 孙昊[2] 苏忠民[2] 王荣顺[2] 

机构地区：[1]海南师范学院化学系,海口571158 [2]东北师范大学化学学院功能材料化学研究所,长春130024

出　　处：《高等学校化学学报》2005年第4期723-726,共4页Chemical Journal of Chinese Universities

基　　金：教育部"跨世纪优秀人才培养计划"基金(批准号:教技函[2001]3);海南省教育厅科研基金(批准号:hjkj200312)资助.

摘　　要：用量子化学密度泛函理论的UB3LYP/6-311+G方法和高级电子相关的UQCISD(T)/6-311+G方法研究了HCCO与CH(2Π)自由基反应的微观机理.采用双水平直接动力学方法IVTST-M和正则变分过渡态理论研究了在1000～2500K温度范围内反应的速率常数.结果表明,HCCO与CH(2Π)双自由基反应过程中存在3个反应通道,生成产物为C2H2+CO.通道2为主要反应路径,通道1也占一定的比例.在所研究的温度范围内,速率常数计算的变分效果均较小,反应为放热反应.The mechanism for the biradical reaction beween HCCO and CH(~ 2Π) was investigated theoretically by using the DFT-UB3LYP/6-311+G~** and the high-level electron-correlation UQCISD(T)/{6-311+G~** } at single-point. The dual-level direct dynamics method was employed to gain the information of potential energy surface for the title reaction. The rate constants were calculated over the range of temperature 1 000-2 500 K by using variational transition-state theory. The results show that the reaction mechanism of the title reaction involves three channels, producing C_2H_2+CO product. Channels 2 and 1 are the favorable routes. It is found that the variational effect for the rate constant calculation is very small in the studied temperature range. The reaction is exothermic.

关 键 词：乙烯酮自由基(HCCO) 反应机理 密度泛函理论(DFT) 变分过渡态 

分 类 号：O641[理学—物理化学]