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Proton transfer and unimolecular decay in the reaction HCO/sup +/ + CH/sub 3/OH. -->. CH/sub 3/OH/sub 2//sup +/ + CO

Journal Article · · J. Phys. Chem.; (United States)
DOI:https://doi.org/10.1021/j100208a022· OSTI ID:6803729
We report a study of the title reaction over the relative energy range from 0.45 to 3.59 eV. The proton-transfer reaction proceeds in a direct, impulsive manner at all energies with 33 to 70% of the available energy appearing in product translation. Dissociation of the protonated methanol product via CH/sub 3//sup +/ formation or elimination of H/sub 2/ to CH/sub 2/OH/sup +/ becomes important at higher collision energies. Measurement of the threshold for CH/sub 3//sup +/ production demonstrates that > 90% of the HCO/sup +/ reagents are in the ground vibrational state. Abnormally small product translational energy release for H/sub 2/ elimination provides evidence that quantum mechanical tunneling through the exit channel barrier determines the dynamics of this process. Isotopic labeling studies, in which the parent ion CH/sub 3/ODH/sup +/ may eliminate H/sub 2/ or HD, show that k/sub H/sub 2///k/sub HD/ = 3.0, confirming the role of tunneling in the elimination step.
Research Organization:
Univ. of Rochester, NY
OSTI ID:
6803729
Journal Information:
J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 86:11; ISSN JPCHA
Country of Publication:
United States
Language:
English