Computational mechanistic investigation of the Fe + CO 2 → FeO + CO reaction.

Autor: Dias Vicentini E; Departamento de Química, Laboratório Computacional de Espectroscopia e Cinética, Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto, Universidade de São Paulo, 14040-901, Ribeirão Preto-SP, Brazil. antoniogsof@ffcrp.usp.br., de Lima Batista AP, Sampaio de Oliveira-Filho AG
Jazyk: angličtina
Zdroj: Physical chemistry chemical physics : PCCP [Phys Chem Chem Phys] 2020 Aug 07; Vol. 22 (29), pp. 16943-16948. Date of Electronic Publication: 2020 Jul 16.
DOI: 10.1039/d0cp00479k
Abstrakt: We report a computational study of the mechanism and determination of the rate constants of the Fe + CO 2 → FeO + CO reaction, in the 1000-3000 K temperature range, at the CCSD(T)/CBS//B3LYP/def2-TZVP level of theory. The overall rate constant was obtained by a Kinetic Monte Carlo simulation. The calculated rate constant, at 2000 K, is 9.72 × 10 -13 cm 3 molecule -1 s -1 , in agreement with experimental measurements: 2.97 × 10 -13 cm 3 molecule -1 s -1 [A. Giesen et al., Phys. Chem. Chem. Phys., 2002, 4, 3665] and 1.13 × 10 -13 cm 3 molecule -1 s -1 [V. N. Smirnov, Kinet. Catal., 2008, 49, 607]. Our study shows that this reaction follows a complex mechanism, with multiple reaction paths contributing to the overall rate, and that CCSD(T) accurately describes this transition metal reaction.
Databáze: MEDLINE