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We present here the instrument design and first experimental results from a multipass millimeter/submillimeter spectrometer designed to probe dissociative reaction dynamics. This work focuses on benchmarking the instrument performance through detection of the CH3O and H2CO products from methanol dissociation induced by a high-voltage plasma discharge. Multiple rotational lines from CH3O and H2CO were observed when this plasma discharge was applied to a sample of methanol vapor seeded in an argon supersonic expansion. The rotational temperature of the dissociation products and their abundance with respect to methanol were determined using a Boltzmann analysis. The minimum detectable absorption coefficient for this instrument was determined to be αmin≤ 5 × 10–9cm–1. We discuss these results in the context of future applications of this instrument to the study of photodissociation branching ratios for small organic molecules that are important in complex interstellar chemistry.

Both grain surface and gas phase chemistry have been invoked to explain the disparate relative abundances of methyl formate and its structural isomers acetic acid and glycolaldehyde in the Sgr B2(N) star-forming region. While a network of grain surface chemistry involving radical-radical reactions during the warm-up phase of a hot core is the most chemically viable option proposed to date, neither qualitative nor quantitative agreement between modeling and observation has yet been obtained. In this study, we seek to test additional grain surface and gas phase processes to further investigate methyl formate-related chemistry by implementing several modifications to the Ohio State University gas/grain chemical network. We added two new gas phase chemical pathways leading to methyl formate, one involving an exothermic, barrierless reaction of protonated methanol with neutral formic acid; and one involving the reaction of protonated formic acid with neutral methanol to form both the cis and trans forms of protonated methyl formate. In addition to these gas phase processes, we have also investigated whether the relative product branching ratios for methanol photodissociation on grains influence the relative abundances of methyl formate and its structural isomers. We find that while the new gas phase formation pathways do not alter the relative abundances of methyl formate and its structural isomers, changes in the photodissociation branching ratios and adjustment of the overall timescale for warm-up can be used to explain their relative ratios in Sgr B2(N).