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Reaction Mechanism and Product Branching Ratios of the OH + C2H3F Reaction: A Theoretical Study
ChihHaoChin
School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China
Abstract:
Ab initio CCSD(T)/CBS//B3LYP/6-311G(d,p) calculations of the potential energy surface for possible dissociation channels of the HOC2H3F with Rice-Ramsperger-Kassel-Marcus (RRKM) calculations of rate constants in order to predict statistical product branching ratios in dissociation of HOC2H3F at various internal energies. The most favorable reaction pathway leading to the major CH2CHO + HF products is the following: OH + C2H3F ? i2 ? TS14 ? i6 ? TS9 ? i3 ? TS3 ? CH2CHO + HF, where the rate-determining step is HF elimination from the CO bridging position via TS11, lying above the reactants by 3.8 kcal/mol. The CH2O + CH2F products can be formed by F atom migration from C? to C? position via TS14, then H migration from O to C? position via TS16, and C-C breaking to form the products via TS5, which is by 1.8 kcal/mol lower in energy than the reactants, but by 4.0 kcal/mol lower than TS11. RRKM calculations have been carried out for the individual rate constants for various channels. The calculations serve as useful estimates for rate constants and reaction paths in applications of combustion and atmospheric modeling regimes, where experimental data are not available.
Key words:  ab initio, potential energy surface, reaction mechanism, RRKM, branching ratio
FundProject:
Reaction Mechanism and Product Branching Ratios of the OH + C2H3F Reaction: A Theoretical Study
ChihHaoChin
School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China
摘要:
Ab initio CCSD(T)/CBS//B3LYP/6-311G(d,p) calculations of the potential energy surface for possible dissociation channels of the HOC2H3F with Rice-Ramsperger-Kassel-Marcus (RRKM) calculations of rate constants in order to predict statistical product branching ratios in dissociation of HOC2H3F at various internal energies. The most favorable reaction pathway leading to the major CH2CHO + HF products is the following: OH + C2H3F ? i2 ? TS14 ? i6 ? TS9 ? i3 ? TS3 ? CH2CHO + HF, where the rate-determining step is HF elimination from the CO bridging position via TS11, lying above the reactants by 3.8 kcal/mol. The CH2O + CH2F products can be formed by F atom migration from C? to C? position via TS14, then H migration from O to C? position via TS16, and C-C breaking to form the products via TS5, which is by 1.8 kcal/mol lower in energy than the reactants, but by 4.0 kcal/mol lower than TS11. RRKM calculations have been carried out for the individual rate constants for various channels. The calculations serve as useful estimates for rate constants and reaction paths in applications of combustion and atmospheric modeling regimes, where experimental data are not available.
关键词:  ab initio, potential energy surface, reaction mechanism, RRKM, branching ratio
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