Acta Phys. -Chim. Sin. ›› 2010, Vol. 26 ›› Issue (02): 441-446.doi: 10.3866/PKU.WHXB20100218

• QUANTUM CHEMISTRY AND COMPUTATION CHEMISTRY • Previous Articles     Next Articles

Spin-Forbidden Reaction Mechanism of CO2 Cleavage Activated by W+ in Gas Phase

LIU Ling-Ling, WANG Yong-Cheng   

  1. College of Chemistry and Environment Science, Lanzhou City University, Lanzhou 730070, P. R. China; College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, P. R. China
  • Received:2009-08-05 Revised:2009-11-25 Published:2010-01-26
  • Contact: WANG Yong-Cheng E-mail:wangyc@nwnu.edu.cn

Abstract:

We investigated the spin-forbidden reaction mechanism of CO2 cleavage, activated by W+ in gas phase, using density functional theory (DFT, UB3LYP) with the relativistic effective core potential (ECP) of basis sets (SDD) for Wand the 6-311+G(3d) basis set forCand O. The calculation results showthatW+ initially closes to CO2 on the sextet surface, then the products, WO+ and CO, exit the channel on the quartet surface. The process involves an intersystem crossing (ISC) from the sextet to the quartet state. We obtained a minimum energy crossing point (MECP) using the algorithm in Harvey method. The large spin-orbital coupling (SOC) constant (494.95 cm-1) calculated shows that the spin-forbidden reaction takes place easily. Furthermore, the overall exothermicity is 122.33 kJ·mol-1.

Key words: Density functional theory, W+activation, Spin-forbidden reaction, Minimumenergy crossing point, Spin-orbital coupling

MSC2000: 

  • O641