Absolute rate constants for the reaction of silyl with nitric oxide, ethylene, propyne, and propylene, and the silyl recombination reaction

Abstract

The kinetics of the reactions SiH3 + SiH3 and SiH3 + NO, SiH3 + C3H6, C3H4, and C2H4 are examined with time-resolved IR diode laser spectroscopy. The use of SiH3Br as a precursor for direct photochemical production of SiH3 at 193 nm is demonstrated. SiH3 is observed to react with NO (k(NO) = (2.5 ± 0.5) × 10-12 cm3 molecule-1 s-1), C3H6 and C3H4 (k(C3H6) = (2.4 ± 0.3) × 10-13 and k(C3H4) ≤ (1.8 ± 0.4) × 10-14 cm3 molecule-1 s-1) but is unreactive toward C2H4 (k(C2H4) ≤ (3 ± 3) × 10-15 cm3 molecule-1 s-1). An upper limit to the bimolecular rate constant for the radical recombination process, SiH3 + SiH3, is determined, krc ≤ (6.1 ± 3.5) × 10-11 cm3 molecule-1 s-1. © 1990.