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Acta Chimica Sinica ›› 2007, Vol. 65 ›› Issue (20): 2203-2210.     Next Articles

RN (R＝CH3, CH3CH2)异构化及脱氢反应的量子拓扑研究

李晓艳1,2，孙政1，孟令鹏1，郑世钧*,1   

  1. (1河北师范大学计算量子化学研究所 石家庄 050016)
    (2中国科学院研究生院化学与化学工程学院 北京 100049)
  • 投稿日期:2007-03-08 修回日期:2007-05-17 发布日期:2007-10-28
  • 通讯作者: 郑世钧

Quantum Topological Studies on the Isomerization and H2 Elimination Reaction of RN (R＝CH3, CH3CH2)

LI Xiao-Yan1,2; SUN Zheng1; MENG Ling-Peng1; ZHENG Shi-Jun*,1   

  1. (1 Institute of Computational Quantum Chemistry, College of Chemistry, Hebei Normal University, Shijiazhuang 050016)
    (2 College of Chemistry and Chemical Engineering, Graduate University of Chinese Academy of Sciences, Beijing 100049)
  • Received:2007-03-08 Revised:2007-05-17 Published:2007-10-28
  • Contact: ZHENG Shi-Jun

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The isomerization reactions of singlet state and triplet state RN (R＝CH3, CH3CH2)→R'NH (R'＝CH2, CH3CH), and hydrogen elimination reactions of RN have been investigated at CASSCF/6-311＋G (d, p) level. The single point energies are obtained at MP2/6-311＋G (d, p) and CCSD/6-311＋G (d, p) levels. The intersystem crossing (ISC) of the singlet and triplet potential surface during the RN (R＝CH3, CH3CH2) isomerization illustrates clearly how the ground-state reactants 3RN (R＝CH3, CH3CH2) transform to ground-state products 1R'NH (R'＝CH2, CH3CH). The topological analysis of electron density shows that there exist two kind of structure transitional structure (STS) in the whole isomerization: a T-shaped conflict STS appears in the singlet isomeration channel and a bifurcation-type ring structure appears in the triplet isomeration channel. The “atom-molecule bond”, which exists in the H2 elimination channel, shows that two hydrogen atoms eliminate from CH3N as a H2 molecule.

Key words: reaction mechanism, electron density of topological analysis, structure transition state, atom-molecule bond