The reaction of methyl radical with nitrogen atom on the triplet potential energy surface: A CCSD(T)/CBS characterization

CCSD(T)/cc-pVnZ (n = D, T, Q) calculations followed by extrapolations to the CBS limit are used to characterize stationary states of species participating in the N(4S) + CH3 (2A′′) reaction on the triplet PES. A mechanistic model is investigated and reaction rates are computed for every step and the overall reaction. Our best CBS estimate (1.93 × 10−10 cm3 molecule−1 s−1) for the overall rate constant leading to the formation of H2CN + H compares well with the experimental values (8.5 × 10−11 and 1.3 × 10−10 cm3 molecule−1 s−1), thus reducing significantly the discrepancy of a previous theoretical result (9.1 × 10−12 cm3 molecule−1 s−1).