2014/06/05 by Robin J. Shannon, Christophe Cossou, Shannon, Robin J. +14
Chemistry · Earth and Planetary Sciences · Physics and Astronomy · #Ab initio #Adduct #Advanced Chemical Physics Studies #Analytical Chemistry (journal) #Astrophysics of Galaxies (astro-ph.GA) #Atmospheric Ozone and Climate #Atom (system on chip) #Atomic physics #Catalysis #Chemical Physics (physics.chem-ph) #Chemical kinetics #Chemistry #FOS: Physical sciences #Fluorescence #Kinetics #Laser-induced fluorescence #Methanol #Molecule #Organic chemistry #Photochemistry #Photodissociation #Physical chemistry #Physics #Reaction rate #Reaction rate constant #Spectroscopy and Laser Applications #astro-ph.GA #physics.chem-ph
paper · pdf · doi:10.48550/arxiv.1406.1363
Accepted to RSC Advances
arxiv created 2014/06/05 · openalex publication_date 2014/06/05 · arxiv updated 2014/06/06 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/05
Rate constants for the C(3P) + CH3OH reaction have been measured in a continuous supersonic flow reactor over the range 50 K to 296 K. C(3P) was created by the in-situ pulsed laser photolysis of CBr4, a multiphoton process which also produced some C(1D), allowing us to investigate simultaneously the low temperature kinetics of the C(1D) + CH3OH reaction. C(1D) atoms were followed by an indirect chemiluminescent tracer method in the presence of excess CH3OH. C(3P) atoms were detected by the same chemiluminescence technique and also by direct vacuum ultra-violet laser induced fluorescence (VUV LIF). Secondary measurements of product H(2S) atom formation have been undertaken allowing absolute H atom yields to be obtained by comparison with a suitable reference reaction. In parallel, statistical calculations have been performed based on ab-initio calculations of the complexes, adducts and transition states (TSs) relevant to the title reaction. By comparison with the experimental H atom yields, the preferred reaction pathways could be determined, placing important constraints on the statistical calculations. The experimental and theoretical work are in excellent agreement, predicting a negative temperature dependence of the rate constant increasing from 2.2 x 10-11 cm3 molecule-1 s-1 at 296 K to 20.0 x 10-11 cm3 molecule-1 s-1 at 50 K. CH3 and HCO are found to be the major products under our experimental conditions. As this reaction is not considered in current astrochemical networks, its influence on interstellar methanol abundances is tested using a model of dense interstellar clouds.