Citation: YU Zhuan-Ni, XU Xiang, XIA Shu-Wei, YU Liang-Min. Density Functional Theoretical Study on the Reaction Mechanism of HOCO and Its Radical[J]. Chinese Journal of Structural Chemistry, ;2015, 34(7): 985-994. doi: 10.14102/j.cnki.0254-5861.2011-0690 shu

Density Functional Theoretical Study on the Reaction Mechanism of HOCO and Its Radical

YU Zhuan-Ni ^a,b ,
XU Xiang ^b ,
XIA Shu-Wei ^a,, ,
YU Liang-Min ^a

a.
a. Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao 266100, China;
b.
b. College of Chemistry and Pharmacy, Qingdao Agricultural University, Qingdao 266109, China

Corresponding author: XIA Shu-Wei,
Received Date: 16 February 2015
Available Online: 15 May 2015
Fund Project: This work was supported by the National Natural Science Foundation of China (50673085,20677053) (50673085,20677053)

In this paper, the reaction mechanism of HOCO with its radical has been investigated deeply by density functional theory (DFT), while the geometries and harmonic vibration frequencies of the reactants, intermediates, transition states and products have been calculated at the B3LYP/6-311++G** level. The CCSD(T)/cc-pVQZ method was used to further calculate the single-point energy of each stationary point along the reaction channel. The result shows that channels (b) and (d) via carbon-carbon intermediates are competing with the ones (e), (f), (i) and (l) through carbon-oxygen intermediates, and the six channels are dominant for the title reaction to produce HCOOH and CO₂. The result also indicates that the hydrogen abstraction from the HOCO radical can be performed quickly by the self-interaction of HOCO in the absence of other radicals or atoms, which indirectly proves for the first time that the ground-state cis-HOCO radical is not decomposed by the tunneling effect. In addition, the charges of natural population analysis (NPA) and the variation of chemical bonds have been analyzed by the Natural Bond Orbital (NBO) method along with the important reaction path.
- HOCO radical,
- self-interaction,
- natural bond orbital analysis,
- tunneling effect
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