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.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.