A theoretical investigation of the primary dissociation paths of ethynylsilane

Abstract

Various mechanisms leading to the dissociation of ethynylsilane have been investigated by ab initio molecular orbital methods. Geometries corresponding to the reactant, transition states, and products have all been optimized at the HF/3-21G and HF/6-31 G* levels of theory. Heats of reaction and barrier heights have been obtained at the MP4SDTQ/6-31G* level. Zero-point energy corrections and harmonic vibrational frequencies have been computed at the HF/3-21G level. These results have been used to calculate unimolecular dissociation rate constants by RRKM theory. This information is then used to reexamine the mechanisms of dissociation for ethynylsilane from previous experimental shock-tube and stirred-flow studies.