The influence of the environment in chemical reactivity: the HCOOH formation from the H2O + CO reaction

Autor(es)

Alves, Esdras ^[1] ; Franco, Mauricio P. ^[2] ; Pilling, Sergio ^[3] ; Machado, Francisco B. C. ^[4] ; Spada, Rene F. K. ^[2]

Afiliação do(s) autor(es)

^[1] Univ Fed Sao Paulo, Inst Ciencia & Tecnol, BR-12031280 Sao Jose Dos Campos, SP - Brazil

^[2] Inst Tecnol Aeronaut, Dept Fis, BR-12228900 Sao Jose Dos Campos, SP - Brazil

^[3] Univ Vale Paraiba, Inst Pesquisa & Desenvolvimento, BR-12244000 Sao Jose Dos Campos, SP - Brazil

^[4] Inst Tecnol Aeronaut, Dept Quim, BR-12228900 Sao Jose Dos Campos, SP - Brazil

• Tipo de documento: Artigo Científico
• Fonte: Journal of Molecular Modeling; v. 27, n. 9 SEP 2021.
• Citações Web of Science: 0

Resumo

The reaction between carbon monoxide and water was studied occurring in an aerosol medium rich in methanol. This environment is plausible for the primitive and prebiotic Earth atmosphere. The chemical environment is expressed in terms of dielectric constant (epsilon) and the chemical system was modeled employing the polarizable continuum model (PCM). The main results were acquired from calculations employing the M06-2X density functional for the electronic structure calculations and the canonical variational theory with small curvature tunneling for the chemical kinetic calculations. The rise of epsilon affects both the thermochemistry and the kinetics of the reaction, increasing the barrier height and decreasing the rate constant for the reaction occurring at room temperature. For example, the rate constant at 300 K is 5-10x 10(- 53) cm(3) .molecule(- 1) .s(- 1) for low dielectric constant (epsilon < 3) and around 2-4x 10(- 53) cm(3) .molecule(- 1) .s(- 1) for epsilon between 7 and 40. Our results indicate that the epsilon variation allows a fine tuning to the rate of the reaction. (AU)

• Processo FAPESP: 19/25105-6 - Hidrocarbonetos aromáticos policíclicos (PAH's): dopagem, vacância, reatividade, estados excitados: uma abordagem multiconfiguracional
• Beneficiário: Francisco Bolivar Correto Machado
• Modalidade de apoio: Auxílio à Pesquisa - Regular
• Processo FAPESP: 19/07671-4 - Estudo teórico de moléculas em ambientes astrofísicos
• Beneficiário: Rene Felipe Keidel Spada
• Modalidade de apoio: Auxílio à Pesquisa - Regular