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Citation: LIU Ling-Ling, WANG Yong-Cheng. Spin-Forbidden Reaction Mechanism of CO₂ Cleavage Activated by W⁺ in Gas Phase[J]. Acta Physico-Chimica Sinica, ;2010, 26(02): 441-446. doi: 10.3866/PKU.WHXB20100218 shu

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

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 Date: 5 August 2009
Available Online: 24 December 2009

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 al rithm 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.
- Density functional theory,
- W+activation,
- Spin-forbidden reaction,
- Minimumenergy crossing point,
- Spin-orbital coupling
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沈阳化工大学材料科学与工程学院沈阳 110142

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

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通讯作者: 陈斌, bchen63@163.com

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