Theoretical study on the reaction CX3 + SiH(CH3)3 (X = H, F)

✍ Scribed by Hui Zhang; Liu Yang; Jing-Yao Liu; Ze-Sheng Li

• Publisher: John Wiley and Sons
• Year: 2011
• Tongue: English
• Weight: 730 KB
• Volume: 33
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.21964

✦ Synopsis

Theoretical investigations are carried out on the multiple-channel reactions, CH 3 þ SiH(CH 3 ) 3 ! products and CF 3 þ SiH(CH 3 ) 3 ! products. The minimum energy paths (MEP) are calculated at the MP2/6-311 þ G(d,p) level, and energetic information is further refined by the MC-QCISD (single point) method. The rate constants for major reaction channels are calculated by the canonical variational transition state theory (CVT) with smallcurvature tunneling (SCT) correction over the temperature range 200-1500 K. The theoretical rate constants are in good agreement with the available experimental data and are found to be k 1a (T) ¼ 1.93 Â 10 À24 T 3.15 exp(À1214.59/T) and k 2a (T) ¼ 1.33 Â 10 À25 T 4.13 exp(À397.94/T) (in unit of cm 3 molecule À1 s À1 ). Our calculations indicate that hydrogen abstraction channel from SiH group is the major channel due to the smaller barrier height among five channels considered. V