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• W2084632738 endingPage "7331" @default.
• W2084632738 startingPage "7321" @default.
• W2084632738 abstract "The dynamics of overtone-excited pyruvic acid (PA) is studied using a combination of experimental and theoretical methods. It is experimentally observed that high overtone excitation of the OH-stretching mode of PA in the gas phase leads to a unimolecular decarboxylation reaction. An RRKM analysis of the rate is consistent with previous experiments for the thermal reaction but is inconsistent with the present overtone chemistry; from this it is concluded that the overtone-induced reaction is likely to be a direct reaction. Using a Fourier transform infrared spectrometer and a cavity ring-down spectrometer, the spectrum for the OH-stretch fundamental and overtone transitions is measured. We assign two conformers of PA in the spectrum, the Tc and Tt, corresponding to distinct orientations of the OH-group. The spectral peaks for the Tc-conformer broaden dramatically at the third and fourth overtones while those of the Tt-conformer remain relatively narrow. Using a three-mode quantum mechanical model for the vibrational states, the line positions and intensities are well reproduced by theory. The line widths, and the associated dynamical interpretation, are provided by a direct dynamics calculation, where the potential is computed on-the-fly and all degrees of freedom are included. It is found that the line broadening is due to the onset of H-atom chattering between the two O-atoms, an effect that occurs for the Tc-conformer but not the Tt-conformer. This H-atom-transfer process is the first step of the decarboxylation reaction mechanism, which subsequently involves breaking the C-C bond. The theoretical and experimental line widths agree but do not correspond to the full reaction time which is much longer than the initial chattering step." @default.
• W2084632738 created "2016-06-24" @default.
• W2084632738 creator A5046342814 @default.
• W2084632738 creator A5051342774 @default.
• W2084632738 creator A5052863796 @default.
• W2084632738 creator A5086087324 @default.
• W2084632738 date "2008-07-19" @default.
• W2084632738 modified "2023-09-25" @default.
• W2084632738 title "Dynamics of Vibrational Overtone Excited Pyruvic Acid in the Gas Phase: Line Broadening through Hydrogen-Atom Chattering" @default.
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• W2084632738 doi "https://doi.org/10.1021/jp803225c" @default.
• W2084632738 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/18637664" @default.
• W2084632738 hasPublicationYear "2008" @default.
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