Photochemistry of carbon monoxide and methanol in water and nitric acid hydrate ices: A NEXAFS study

Physical Chemistry Chemical Physics : PCCP
C LaffonPh Parent

Abstract

Soft X-ray induced chemistry of H(2)O, CO and CH(3)OH and the effects of the water and nitric acid hydrate (HNO(3).1.65H(2)O) matrix on the photochemistry of CO and CH(3)OH have been investigated using NEXAFS spectroscopy. For pure H(2)O, CO and CH(3)OH ices, we show that the destruction rates are strongly limited by back reactions, leading to strikingly high survival rates of these molecules upon the harsh irradiation conditions to which they are submitted. We also evidence the interplay between the photochemical reactions of CO and CH(3)OH and those of the matrix. The OH and O radicals released by the photolysis of H(2)O and HNO(3) react with the CO and CH(3)OH and their fragments, considerably reducing the survival rates compared to pure CO and pure CH(3)OH ices, especially in presence of nitric acid, and dramatically enhancing the formation of CO(2) at the expense of CO. Because NEXAFS spectroscopy allows identifying which reactions are important among those possible, it emerges a simple picture of the photochemical routes of CO and CH(3)OH in the H(2)O and HNO(3)/H(2)O environments.

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Citations

Nov 28, 2013·Chemical Reviews·Chris J BennettThomas M Orlando
Jan 28, 2014·Journal of the American Chemical Society·Gérôme MelaetGabor A Somorjai
Jun 7, 2011·The Journal of Chemical Physics·George Tzvetkov, Falko P Netzer
Dec 13, 2012·Physical Chemistry Chemical Physics : PCCP·M AlagiaS Stranges
Apr 25, 2019·Journal of Chemical Theory and Computation·Katherine J OosterbaanMartin Head-Gordon

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