Marcelo André Petry Pontes, Edson Firmino Viana de Carvalho, Luiz Fernando de Araujo Ferrão, Francisco Bolivar Correto Machado, Orlando Roberto-Neto
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Rate Constants and Energetics of the H2SiO + H Reaction System: RP-VTST/MT and VRC Calculations
Silaformaldehyde (H2SiO) is one of the components of the kinetics roadmap of silane oxidation. For this species, kinetics decomposition is related to three elementary reactions, that is, H + H2SiO → H2 + HSiO (R1), H + H2SiO → H2SiOH (R2), and H + H2SiO → H3SiO (R3). To improve the kinetics of these reaction systems, accurate energetics were computed with the ωB97X-D and CCSD(T) methods, and the rate constants were determined using CVT methods with multidimensional tunneling. KIEs were also determined for (R1), which is an important path at high temperatures. At the ωB97X-D/aug-cc-pVTZ level, the value of electronic barrier height is 4.5, 5.2, and 0.4 kcal mol−1 for (R1), (R2), and (R3), respectively. In addition to the characterization of the elementary reactions, a mechanism consisting of all interconnected reactions was characterized by using the energy-grained master equation approach to determine the phenomenological rate constants for the formation of products and the time evolution of the species. Up to 500 K, the main reaction product is H2SiOH, while the bimolecular products H2 + HSiO dominate at higher temperatures.
期刊介绍：
This distinguished journal publishes articles concerned with all aspects of computational chemistry: analytical, biological, inorganic, organic, physical, and materials. The Journal of Computational Chemistry presents original research, contemporary developments in theory and methodology, and state-of-the-art applications. Computational areas that are featured in the journal include ab initio and semiempirical quantum mechanics, density functional theory, molecular mechanics, molecular dynamics, statistical mechanics, cheminformatics, biomolecular structure prediction, molecular design, and bioinformatics.
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