Dual-level direct dynamics studies for the reactions of dimethyl ether with hydrogen atom and methyl radical

✍ Scribed by Jia-Yan Wu; Jing-Yao Liu; Ze-Sheng Li; Xu-Ri Huang; Chia-Chung Sun

• Publisher: John Wiley and Sons
• Year: 2003
• Tongue: English
• Weight: 120 KB
• Volume: 24
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.10219

✦ Synopsis

Abstract

The dual‐level direct dynamics approach is employed to study the dynamics of the CH~3~OCH~3~ + H (R1) and CH~3~OCH~3~ + CH~3~ (R2) reactions. Low‐level calculations of the potential energy surface are carried out at the MP2/6‐311+G(d,p) level of theory. High‐level energetic information is obtained at the QCISD(T) level of theory with the 6‐311+G(3df,3pd) basis set. The dynamics calculations are performed using variational transition state theory (VTST) with the interpolated single‐point energies (ISPE) method, and small‐curvature tunneling (SCT) is included. It is shown that the reaction of CH~3~OCH~3~ with H (R1) may proceed much easier and with a lower barrier height than the reaction with CH~3~ radical (R2). The calculated rate constants and activation energies are in good agreement with the experimental values. The calculated rate constants are fitted to k~R1~ = 1.16 × 10^−19^ T^3^ exp(−1922/T) and k~R2~ = 1.66 × 10^−28^ T^5^ exp(−3086/T) cm^3^ mol^−1^ s^−1^ over a temperature range 207–2100 K. Furthermore, a small variational effect and large tunneling effect in the lower temperature range are found for the two reactions. © 2003 Wiley Periodicals, Inc. J Comput Chem 24: 593–600, 2003