OH + HONO reaction: A theoretical study
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- 作者：De-Quan Wang ; Ji-Lai Li ; Xu-Ri Huang ; Cai-Yun Geng ; Chia-Chung Sun
- 关键词：Reaction mechanism ; Potential energy surface ; OH radical ; HONO
- 刊名：Journal of Molecular Structure: THEOCHEM
- 出版年：2007
- 出版时间：20 December 2007
- 年：2007
- 卷：847
- 期：1-3
- 页码：10-22
- 全文大小：3996 K
文摘
The reaction of OH radical with nitrous acid HONO is investigated by ab initio quantum chemistry methods. The doublet potential energy surfaces are calculated at the CCSD(T)/aug-cc-pVDZ//UMP2/6-311++G(d,p) levels. Various possible reaction pathways are considered. Among them, the most feasible pathway should be the OH radical attacking on the hydrogen of cis-HONO to form a 6-member-ring complex C2 barrierlessly, followed by the indirect hydrogen abstraction transition state TSabsC2-C6I to form a weakly bound complex C6, giving rise to the educts P1 H2O + NO2. Because all of the complexes, transition state, and products involved in the feasible pathway lie below the reactants, the title reaction is expected to be rapid, which in good agreement experiment. The present study may be helpful for probing the mechanisms of the HONO reactions and understanding the atmospheric chemistry.