Theoretical and kinetic study of the H + C2H5CN reaction

✍ Scribed by Jingyu Sun; Yizhen Tang; Hao Sun; Xiujuan Jia; Xiumei Pan; Rongshun Wang

• Publisher: John Wiley and Sons
• Year: 2009
• Tongue: English
• Weight: 374 KB
• Volume: 31
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.21397

✦ Synopsis

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. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010