Detailed benchmark ab initio mapping of the potential energy surfaces of the X + C2H6 [X = F, Cl, Br, I] reactions

We investigate three reaction pathways of the X + C 2 H 6 [X = F, Cl, Br, I] reactions: H-abstraction, methyl-substitution, and H-substitution, with the latter two proceeding via either Walden-inversion or front-side-attack mechanisms. We report classical and adiabatic relative energies of unprecede...

Full description

Saved in:
Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2019, Vol.21 (1), p.396-48
Main Authors: Papp, Dóra, Gruber, Balázs, Czakó, Gábor
Format: Article
Language:English
Subjects:
Benchmarks
Channels
Enthalpy
Entrances
Exothermic reactions
Mapping
Potential energy
Spin-orbit interactions
Substitution reactions
Citations: Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:We investigate three reaction pathways of the X + C 2 H 6 [X = F, Cl, Br, I] reactions: H-abstraction, methyl-substitution, and H-substitution, with the latter two proceeding via either Walden-inversion or front-side-attack mechanisms. We report classical and adiabatic relative energies of unprecedented accuracy for the corresponding stationary points of the reaction potential energy surfaces (PESs) by augmenting the CCSD(T)-F12b/aug-cc-pVQZ energies by core-correlation, post-CCSD(T) and spin-orbit corrections. Taking these correction terms into account turns out to be essential to reach subchemical, i.e.
ISSN:1463-9076
1463-9084
DOI:10.1039/c8cp06445h