Quantum chemical study of the mechanism for OH-initiated atmospheric oxidation reaction of (Z)-CF₃CFCHF

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• 作者：Weichao Zhang ; ^{zwc@xznu.edu.cn} ; Benni Du
• 关键词：(Z)-CF3CFCHF ; OH radical ; Reaction mechanism ; CBS-QB3
• 刊名：Computational and Theoretical Chemistry
• 出版年：2012
• 期刊代码：pc22_2210271X
• 类别：ch
• 出版时间：1 July, 2012
• 卷：991
• 期：Complete
• 页码：22-31
• 文件大小：1793 K

摘要

The mechanism and products of the reaction of (Z)-CF₃CFCHF with OH radical in the absence and presence of O₂/NO have been elucidated by performing high-level quantum chemistry calculations. The geometries of the reactants, intermediates, transition states, and products are optimized at the B3LYP/6-311++G(d,p) level, and their single point energies are refined at the CBS-QB3 level. Energies for several species are also recalculated at the G3 level. The calculations indicate that the reaction predominantly proceeds via the addition of OH radical to the double bond rather than the direct abstractions of the H and F atoms in (Z)-CF₃CFCHF. The nascent adducts CF₃CFC(OH)HF (IM1) and CF₃C(OH)FCHF (IM2) can either undergo subsequent isomerization and dissociation reactions or further react with O₂/NO. The theoretical results show that the major products are HC(O)F and CF₃C(O)F in both the absence and presence of O₂/NO, which are in good agreement with the experimental finding.