Multichannel RRKM-TST and CVT Rate Constant Calculations for Reactions of CH2OH or CH3O with HO2

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• 作者：S. Hosein Mousavipour ; Zahra Homayoon
• 刊名：Journal of Physical Chemistry A
• 出版年：2011
• 出版时间：April 21, 2011
• 年：2011
• 卷：115
• 期：15
• 页码：3291-3300
• 全文大小：975K
• 年卷期：v.115,no.15(April 21, 2011)
• ISSN：1520-5215

文摘

The kinetics and mechanism of the gas-phase reactions between hydroxy methyl radical (CH₂OH) or methoxy radical (CH₃O) with hydroproxy radical (HO₂) have been theoretically investigated on their lowest singlet and triplet surfaces. Our investigations indicate the presence of one deep potential well on the singlet surface of each of these systems that play crucial roles on their kinetics. We have shown that the major products of CH₂OH + HO₂ system are HCOOH, H₂O, H₂O₂, and CH₂O and for CH₃O + HO₂ system are CH₃OH and O₂. Multichannel RRKM-TST calculations have been carried out to calculate the individual rate constants for those channels proceed through the formation of activated adducts on the singlet surfaces. The rate constants for direct hydrogen abstraction reactions on the singlet and triplet surfaces were calculated by means of direct-dynamics canonical variational transition-state theory with small curvature approximation for the tunneling.