Theoretical and kinetic study of the H + C2H5CN reaction

Abstract

The reaction of H radical with C(2)H(5)CN has been studied using various quantum chemistry methods. The geometries were optimized at the B3LYP/6-311+G(d,p) and B3LYP/6-311++G(2d,2p) levels. The single-point energies were calculated using G3 and BMC-CCSD methods based on B3LYP/6-311++G(2d,2p) geometries. Four mechanisms were investigated, namely, hydrogen abstraction, C-addition/elimination, N-addition/elimination and substitution. The kinetics of this reaction were studied using the transition state theory and multichannel Rice-Ramsperger-Kassel-Marcus methodologies over a wide temperature range of 200-3000 K. The calculated results indicate that C-addition/elimination channel is the most feasible over the whole temperature range. The deactivation of initial adduct C(2)H(5)CHN is dominant at lower temperature with bath gas H(2) of 760 Torr; whereas C(2)H(5)+HCN is the dominant product at higher temperature. Our calculated rate constants are in good agreement with the available experimental data.