Kinetic studies of the reaction of Cl atoms with SiH4
Abstract
The reaction kinetics of chlorine atoms with silane has been studied over the temperature range 273–363 K using the very low pressure reactor technique. The reaction proceeds via a hydrogen-atom abstraction and leads to SiH3 and HCl products. The absolute rate constant was found to be independent of temperature with a value k1=(3.25 ± 0.40)× 10–10 cm3 molecule–1 s–1. Ab initio calculations at the MP2/6–311G(d,p) level of theory did not show any evidence for the formation of an intermediate SiH4–Cl adduct. The thermochemical version of conventional transition-state theory indicated that the transition-state geometry is almost linear, with a Si—H—Cl angle of ca. 170°.