Absorption cross sections and solar photodissociation rates of deuterated isotopomers of methanol

Physics – Space Physics

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Atmospheric Composition And Structure: Chemical Kinetic And Photochemical Properties, Atmospheric Composition And Structure: Evolution Of The Atmosphere, Atmospheric Composition And Structure: Planetary Atmospheres (5405, 5407, 5409, 5704, 5705, 5707)

Scientific paper

Photoabsorption cross sections of CH3OH, CH3OD, CD3OH, and CD3OD are determined in the spectral region 165-220 nm using synchrotron radiation as a light source. Excitation of methanol isotopomers in this wavelength region breaks mainly the O-H or O-D bond to form H or D, respectively. Significantly smaller absorption cross sections near the threshold region are observed for CH3OD and CD3OD. These data are used to calculate corresponding photodissociation rates by the solar flux at 1 AU. The rates for CH3OD and CD3OD are only about 80% and 82% of those for CH3OH and CD3OH, respectively. The effective photo-induced isotopic enrichment factors (per mil) are estimated to be 199‰ for CH3OD, -35‰ for CD3OH, and 154‰ for CD3OD. Such large enrichment factors are expected to induce detectable H/D fractionation in comets or elsewhere if the photo-induced isotopic fractionation effect is important in controlling methanol chemistry.

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