Affiliation:
1. MTA-SZTE Lendület Computational Reaction Dynamics Research Group, Interdisciplinary Excellence Centre and Department of Physical Chemistry and Materials Science, Institute of Chemistry, University of Szeged, Rerrich Béla tér 1, Szeged H-6720, Hungary
Abstract
Reactions between methanol and the hydroxyl radical are of significant interest for combustion-, atmospheric-, and astrochemistry. While the two primary product channels (the formation of H2O with either CH3O· or ·CH2OH) have been the subject of numerous studies, the possibility of other products has seen little attention. Here, we present a comprehensive thermochemical survey of the stationary points and plausible products of the reaction, featuring 29 geometries optimized at the UCCSD(T)-F12b/aug-cc-pVTZ level, followed by accurate composite ab initio computations for all stationary points (including ·CH2OH dissociation and isomerization) and five product channels, with a detailed evaluation of basis set convergence and efficiency. The computations reveal that the formation of methanediol and the hydroxymethoxy radical is thermodynamically favorable and the endothermicity of formaldehyde formation is low enough to be a plausible product channel. We also observe unexpectedly large energy deviations between the partially-spin-adapted ROHF-RCCSD(T) method and ROHF-UCCSD(T) as well as between UHF-UCCSDT(Q) and ROHF-UCCSDT(Q) results.
Funder
National Research, Development and Innovation Office
Ministry of Human Capacities, Hungary
Ministry of Innovation and Technology of Hungary
Momentum Program of the Hungarian Academy of Sciences
KIFU
Subject
Physical and Theoretical Chemistry,General Physics and Astronomy
Cited by
2 articles.
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