Abstract
Reaction ergodography using IRC (intrinsic reaction coordinate) as a unique reaction path is studied for silicon nitride bond formation in the gas phase. This is a dehydrogenation reaction. Using a model system, we have obtained the activation energy 55.4 kcal/mol and the exothermic energy 2.8 kcal/mol (CISD+QC/6-31G{sup **}//HF/6-31G{sup *}). This is consistent with the experimentally observed activation energy 39 kcal/mol by Vasilyeva, Ginovker, Popov, and Repinsky (Izv. Sib. Otd. Akad. Nauk SSSR, Ser. Khim. Nauk 1979, 5, 54). The IRC reveals mode-specific vibrational excitation of SiH{sub 4} in the early stage of reaction, and additionally, that of NH{sub 3} just before the transition state, and successive strong charge-transfer interaction in the neighborhood of the transition state. The first finding is in agreement with the recent observations that 10.6 {mu}m (943.4 cm{sup {minus}1}) light emitted from CO{sub 2} laser is efficient for silicon nitride bond formation in the gas phase.
Published Version
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