摘要
应用量子化学密度泛函理论(DFT)对亚乙烯基自由基(.C2H2)和3O2的反应历程进行计算,在B3LYP/6-311++G(d,p)基组水平下优化了过渡态,中间体和产物的几何构型,并对其振动频率和零点振动能(EZPV)进行计算.结果表明,该反应是一个复杂反应,反应物3O2进攻.C2H2的边端C形成了加合产物H2CCOO(INT1),由H2CCOO经过不同的反应通道得到了不同的产物P1(CH2+CO2),P2(CH2CO+O),P3(CH2O+CO),P4(HCO+HCO),P5(H+CO+HCO),与实验所得的反应产物一致.H2CCOO(INT1)通过异构化生成的H2CC(O)O(INT2),以及进一步生成的H2C(O)CO(INT4)是反应能够进行并生成P3,P4,P5的关键.P1为主要产物,而生成产物P3,P4,P5的多条通道中也存在主要反应通道.
The reaction of vinylidene radical with oxygen was studied systematically by using the density function theory（DFT）.The geometries of stationary points were optimized at B3LYP/6-311＋＋G（d,p） level,the vibration frequencies and zero point vibration energies（ZPVE） have been calculated.The results suggest that the reaction is a complex system,O-atom of oxygen attacks the side C-atom of vinylidene to form the isomer H2CCOO,the isomer undergoes different channels and form five produces which consistent with the experimental results P1（CH2＋CO2）,P2（CH2CO＋O）,P3（CH2O＋CO）,P4（HCO＋HCO）,P5（H＋CO＋HCO）.Because of the different intermediates related,there are more than one channel to generate the products P3,P4,P5.H2CC（O）O（INT2） which is the rotational isomerization product of H2CCOO（INT1） and the further product H2C（O）CO（INT4） are the keys to keeping reaction going on and generating P3,P4,P5.The analysis of reaction barrier calculation indicated that the P1 is the main products,meanwhile,there are more than enough competition channels for forming product P3,P4,P5.
出处
《宁夏大学学报（自然科学版）》
CAS
北大核心
2010年第4期372-376,共5页
Journal of Ningxia University(Natural Science Edition)
基金
宁夏大学科学研究基金资助项目(NDZR10-23)
