Reliable Theoretical Procedures for Calculating the Rate of Methyl Radical Addition to Carbon−Carbon Double and Triple Bonds

Geometries, frequency factors, barriers, and reaction enthalpies have been calculated at a variety of levels of theory for methyl radical addition to CH2CH2, CH2CHCH3, CH⋮CH and CH⋮CCH3, with a view to selecting reliable computational procedures for studying radical addition to carbon−carbon double and triple bonds. Reaction rates for both the addition and reverse (β-scission) reactions were also calculated using various transition-state-theory-based procedures, applied at a number of theoretical levels. In general it was found that the geometries, frequency factors and temperature corrections are relatively insensitive to the level of theory, but barriers and reaction enthalpies require a careful choice of theoretical level. Nonetheless, suitable lower-cost alternatives to the high-level W1 results are provided by G3X-RAD and G3(MP2)-RAD. Although errors are somewhat increased, the RMP2/6-311+G(3df,2p) (for addition to alkenes) or B3-LYP/6-311+G(3df,2p) (for addition to alkynes) levels of theory also pro...