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Issue 26, 2020
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Benchmark ab initio characterization of the abstraction and substitution pathways of the OH + CH4/C2H6 reactions

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Abstract

We report a comprehensive ab initio investigation of the OH + CH4/C2H6 reactions using a high-level composite approach based on CCSD(T)-F12b/aug-cc-pVTZ geometries and CCSD(T)-F12b/aug-cc-pVnZ n = 5/Q energies augmented with additive corrections of post-CCSD(T) correlation, core correlation, scalar relativity, spin–orbit coupling, and zero-point energy. Besides the hydrogen-abstraction (HA) channel leading to H2O + CH3/C2H5H0 = −14.37/−18.19 kcal mol−1), we reveal, for the first time, hydrogen-substitution (HS) and methyl-substitution (MS) pathways resulting in H + CH3OH/C2H5OH (ΔH0 = 13.19/7.12 kcal mol−1) and CH3 + CH3OH (ΔH0 = −2.20 kcal mol−1) products, respectively. The adiabatic barrier heights for HA, MS, and HS in OH + CH4/C2H6 are 4.78/2.18, 39.60, 43.53/41.73(52.48) kcal mol−1, respectively, where substitution proceeds with Walden-inversion or (front-side-attack retention). In the entrance channels van der Waals wells with depths of 0.5–0.8 kcal mol−1 are found and in the exit channels the HOH⋯C2H5, HOH⋯CH3, H3C⋯CH3OH, and H⋯C2H5OH complexes are characterized with De values of 2.4, 1.7, 0.7, and 0.3 kcal mol−1, respectively.

Graphical abstract: Benchmark ab initio characterization of the abstraction and substitution pathways of the OH + CH4/C2H6 reactions

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Article information


Submitted
11 May 2020
Accepted
22 Jun 2020
First published
23 Jun 2020

This article is Open Access

Phys. Chem. Chem. Phys., 2020,22, 14560-14569
Article type
Paper

Benchmark ab initio characterization of the abstraction and substitution pathways of the OH + CH4/C2H6 reactions

B. Gruber and G. Czakó, Phys. Chem. Chem. Phys., 2020, 22, 14560
DOI: 10.1039/D0CP02560G

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