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Hydrogen Atom Abstraction Reaction from Silane with Hydrogen and Methyl Radicals: Rate Constants and Kinetic Isotopic Effects

Year: 2024

Type: article

Abstract: High Resolution Image Download MS PowerPoint Slide The thermal rate constants and H/D kinetic isotope effects (KIEs) of the reactions SiH 4 + H → SiH 3 + H 2 and SiH 4 + CH 3 → SiH 3 + CH 4 were calculated with the variational transition state theory including multidimensional tunneling corrections (VTST-MT). The ωB97X-D and CCSD(T) methods were employed to compute the barrier height and reaction energy. The ωB97X-D/aug-cc-pVTZ methodology was used to build reaction paths, and the CCSD(T)/CBS Q-5 approach was used to improve the energetics of the stationary points in the calculations of CVT/μOMT thermal rate constants. For the SiH 4 + H pathway, the CVT/μOMT rate constants and H/D KIEs are in excellent agreement with previous experimental and theoretical calculations; otherwise, for the SiH 4 + CH 3 pathway, which has few experimental and theoretical data available, it has provided, for the first time, rate constants and kinetic isotope effects using variational transition state theory with multidimensional tunneling corrections.

Source: The Journal of Physical Chemistry A

DOI: 10.1021/acs.jpca.4c05382

Authors: Filipe G. Kano, Edson F. V. de Carvalho, Luiz F. A. Ferrão, Orlando Roberto-Neto, Francisco B. C. Machado

Institutions: Instituto Tecnológico de Aeronáutica, Universidade Federal do Maranhão, Instituto de Estudos Avançados da Universidade de São Paulo

Language: English

Topic: Advanced Chemical Physics Studies

Subfield: Atomic and Molecular Physics, and Optics

Field: Physics and Astronomy

Domain: Physical Sciences

Open Access status: hybrid

Funders: Fundação de Amparo à Pesquisa do Estado de São Paulo, Coordenação de Aperfeiçoamento de Pessoal de Nível Superior, Conselho Nacional de Desenvolvimento Científico e Tecnológico, Fundação de Amparo à Pesquisa e ao Desenvolvimento Científico e Tecnológico do Maranhão