Theoretical study and rate constants calculation for the reactions of SiH3 radical with SiH3CH3 and SiH2(CH3)2

✍ Scribed by Hui Zhang; Gui-Ling Zhang; Jing-Yao Liu; Miao Sun; Bo Liu; Ze-Sheng Li

• Publisher: John Wiley and Sons
• Year: 2009
• Tongue: English
• Weight: 211 KB
• Volume: 31
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.21326

✦ Synopsis

Abstract

The multiple‐channel reactions SiH~3~ + SiH~3~CH~3~ → products and SiH~3~ + SiH~2~(CH~3~)~2~ → products are investigated by direct dynamics method. The minimum energy path (MEP) is calculated at the MP2/6‐31+G(d,p) level, and energetic information is further refined by the MC‐QCISD method. The rate constants for individual reaction channels are calculated by the improved canonical variational transition state theory (ICVT) with small‐curvature tunneling (SCT) correction over the temperature range of 200–2400 K. The theoretical three‐parameter expression k~1~(T) = 2.39 × 10^−23^T^4.01^exp(−2768.72/T) and k~2~(T) = 9.67 × 10^−27^T^4.92^exp(−2165.15/T) (in unit of cm^3^ molecule^−1^ s^−1^) are given. Our calculations indicate that hydrogen abstraction channel from SiH group is the major channel because of the smaller barrier height among eight channels considered. © 2009 Wiley Periodicals, Inc. J Comput Chem 2010