PHOTODISSOCIATION OF FORMIC ACID ISOLATED IN SOLID PARAHYDROGEN

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2011

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Ohio State University

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The \textit{in situ} photochemistry of dopant molecules isolated in solid parahydrogen (pH2) typically differs from analogous studies in rare gas crystals for two main reasons: (1) solid pH2 has a negligible cage effect so that photodissociation of a precursor molecule can lead efficiently to well-separated fragments, and (2) radical fragments can potentially react with the pH2 matrix. Our group is currently studying the 193 nm photochemistry of a number of precursor molecules isolated in solid pH2 via high-resolution FTIR spectroscopy. In this talk I will present results for the 193 nm photolysis of formic acid (FA) in solid pH2. In rare gas matrices, the analogous FA photochemistry proceeds via the CO+H2O and CO2+H2 photodissociation channels.s\ddot{a}Extra close brace or missing open bracenen, \textit{J. Mol. Struct. }\textbf{436-437}, 349 (1997).} In solid pHnen, \textit{J. Mol. Struct. }\textbf{436-437}, 349 (1997).} In solid pH_2$, in addition to these channels we observe the production of HCO and HOCO. Further, after the UV laser is turned off, the HOCO concentration continues to increase with a slow first-order rate constant for a period of 10 hours. At this point, we still do not have a full explanation of the chemical mechanism leading to the post-photolysis increase in the HOCO concentration.

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Author Institution: Department of Chemistry, University of Wyoming, Laramie, WY 82071-3838

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