Acta Phys. -Chim. Sin. ›› 2011, Vol. 27 ›› Issue (03): 564 -570.doi: 10.3866/PKU.WHXB20110308

• THEORETICAL AND COMPUTATIONAL CHEMISTRY • Previous Articles     Next Articles

Mechanisms and Kinetics of the HOSO+NO Reaction

LI Xiao-Yan, LIU Qun, ZHENG Shi-Jun, MENG Ling-Peng   

  1. College of Chemistry and Material Science, Hebei Normal University, Shijiazhuang 050016, P. R. China
  • Received:2010-09-20 Revised:2010-12-07 Published:2011-03-03
  • Contact: MENG Ling-Peng E-mail:menglp@mail.hebtu.edu.cn
  • Supported by:

    The project was supported by the the National Natural Science Foundation of China (20973053, 20771033, 20801017), Natural Science Foundation of Hebei Province, China (B2010000371, B2011205058), Education Department Foundation of Hebei Province, China (2009137), and Foundation of Hebei Normal Univeristy, China (L2008B06, L2009Y06).

Abstract:

The mechanism of the reaction between HOSO and NO was investigated at the B3LYP/6-311++G(d,p) level of theory. The geometries of the reactants, intermediates, transition states, and products were optimized. The intrinsic reaction coordinates (IRC) were traced and the connecting relationship between the transition states and the reactants, products were confirmed. The single point energies of the species were corrected at the CCSD(T) /6-311++G(d,p) level of theory. The reaction rate constants were calculated over a temperature range of 200-3000 K using classical transition state theory (TST) and canonical vibration transition state theory (CVT) combined with a small-curvature tunneling (SCT) correction. The results showed that the HOSO+NO reaction occurs in both the singlet and triplet reaction channels. The singlet reaction channel is dominant, and HNO and SO2 are the main products. The chemical bond changes in the main reaction channel were analyzed by a topological analysis of the electron density.

Key words: HOSO, Reaction mechanism, Rate constant, Topological analysis of electron density

MSC2000: 

  • O641