Ab Initio Chemical Kinetics for Oxidation of CH₃OH by N₂O₄: Elucidation of the Mechanism for Major Product Formation and Its Relevancy to Tropospheric Chemistry.

ABSTRACT: Next to CH₄, CH₃OH is the most abundant C₁ organics in the troposphere. The redox reaction of CH₃OH with N₂O₄ had been shown experimentally to produce CH₃ONO, instead of CH₃ONO₂. The mechanism for the reaction remains unknown to date. We have investigated the reaction by ab initio MO calculations at the UCCSD(T)/6-311+G(3df,2p)//UB3LYP/6-311+G(3df,2p) level. The result indicates that the reaction takes place primarily by the isomerization of N₂O₄ to ONONO₂ through a very loose transition state within the N₂O₄-CH₃OH collision complex with a 14.3 kcal/mol barrier, followed by the rapid attack of ONONO₂ at CH₃

SUBMITTER: Trac HP 

PROVIDER: S-EPMC11264261 | biostudies-literature | 2024 Jul

REPOSITORIES: biostudies-literature