采用MP2(Full), B3LYP, QCISD/MP2方法在6-311G(d, p)水平上对Cl原子与HNCO反应的微观机理进行了理论研究.采用MP2(Full)和B3LYP对反应位能面上的各驻点进行几何构型的全优化,振动分析和IRC计算证实了中间体和过渡态的真实性和相互连接关系.3种方法计算得到了几个反应通道的反应活化能.研究表明,Cl原子进攻HNCO中的H原子为反应的主要反应通道.
[1] 石土金, 李宗和, 刘若庄, Shi Tujin, Li Zonghe, Liu Ruozhuang. HNCO+OH→H2O+NCO的反应机理 [J]. 物理化学学报 1999.
[2] 冀永强, 冯文林, 徐振峰, 雷鸣, 郝茂荣. 氢转移反应HNCO+CHx(x=1～3)的MP2和QCISD计算研究 [J]. 化学学报 2002.doi:10.3321/j.issn:0567-7351.2002.07.005
[3] 刘朋军, 潘秀梅, 赵岷, 孙昊, 苏忠民, 王荣顺. HNCO与CX(X=F, Cl, Br)自由基反应机理的密度泛函理论研究 [J]. 化学学报 2002.doi:10.3321/j.issn:0567-7351.2002.11.007
[4] GLARBORG P, KRISTENSEN P G, JENSEN S H. A flow reactor study of HNCO oxidation chemistry [J]. Combustion and Flame 1994, 98(03).
[5] Sengupta D., Nguyen MT.. MECHANISM OF NH2+CO2 FORMATION IN OH+HNCO REACTION - RATE CONSTANT EVALUATION VIA AB INITIO CALCULATIONS AND STATISTICAL THEORY [J]. The Journal of Chemical Physics 1997, 23(23).
[6] BROWN S S, BERGHOUT H L, CRIM F F. Internal energy distribution of the NCO fragment from near-threshold photolysis of isocyanic acid, HNCO [J]. Journal of Physical Chemistry 1996, 100(19).
[7] Ephraim Woods III, Christopher M. Cheatum, F. Fleming Crim. Using stretching and bending vibrations to direct the reaction of Cl atoms with isocyanic acid (HNCO) [J]. The Journal of Chemical Physics 1999, 13(13).
[8] Zhen-Feng Xu, Jia-Zhong Sun. Theoretical Study on the Reaction Path and Variational Rate Constant of the Reaction HNCO + NH → NCO + NH_2 [J]. The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory 1998, 7(7).
[9] FRISCH M J, TRUCHKS G W, SCHLEGEL H B, Johnson B G, Robb M A, Cheeseman J R. Gaussian94(RevisionD.1) [M]. Gaussian, Inc., Pittsburgh PA 1995.
