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Reaction kinetics of radical isomerization and decomposition of three small unsaturated methyl esters of methyl acrylate (MA, C₄H₆O₂), methyl butenoate (MB, C₅H₈O₂) and methyl crotonate (MC, C₅H₈O₂) are systematically studied with high-level quantum chemistry computation. MB and MC are isomers with the C=C double bonds at different positions. The potential energy profiles for these reactions are obtained at the DLPNO-CCSD(T)/CBS(T-Q)//M062X/ma-TZVP level of theory, and the thermodynamics of the involved species are derived at the CCSD(T)/CBS(T-Q) level of theory using the atomization enthalpy method. Our results show that isomerization reactions with stable cyclic transition states have lower reaction barrier heights, making them energetically and kinetically favored. For decomposition reactions, C–C β-scission reactions are more energetically favorable than C–H β-scission reactions, and the C …