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Michelle R. Brann

Publications and source records attributed to Michelle R. Brann.

2 recordsLinked to original sources

CO and N2 Produced from H2O, CO2, and NH3 Cometary Ice Analogs

Hypervolatile species such as carbon monoxide (CO) and molecular nitrogen (N2) have been detected in comets, and could be used to constrain comet formation temperature conditions if their presence is due to freeze-out and/or entrapment. Here we instead explore another plausible origin of cometary hypervolatiles: photodissociation of less volatile species. We characterize CO and N2 formation following ultraviolet (UV) irradiation and electron bombardment of carbon dioxide (CO2), ammonia (NH3), H2O:CO2, H2O:NH3, and H2O:CO2:NH3 cometary ice analogs. We find that CO and N2 form in all photoprocessed ices at temperatures between 10 K and 100 K, resulting in 0.4-0.9 % CO and 0.03-0.7 % N2 relative to water, and CO/CO2 and N2/NH3 mixing ratios of 2.5-62 % and 0.7-9 %, respectively, across the experiments. Because our initial ices are reasonably well-matched to interstellar ices and we use UV exposure similar to a dark cloud, we can compare the resulting ratios directly to cometary abundances. Such a comparison shows that while only a few of CO observations in comets are readily explained by photodissociation, almost all observed cometary N2 can be accounted for by photodissociation of NH3 embedded in water ice. The latter result is also consistent with observed similarly elevated isotopic ratios of N2 and NH3 in 67P. Taken together, our results suggest that N2/H2O ratios less than 1 % should be used cautiously when inferring a comet's formation location, while the more substantial CO abundances seen in many comets do likely imply entrapment at low ice temperatures.

astro-ph.EP

Methyl Isocyanate Formation from Oxygen Insertion in Methyl Cyanide Ices

In cold molecular clouds, UV photolysis of icy grain mantles generates radicals that lead to new molecule formation. When radical diffusion is limited by low temperatures, oxygen atom addition and insertion reactions, enabled by photolysis of common ice components such as H$_2$O, CO$_2$, CO, and O$_3$, offer an alternative route to chemical complexity through the production of metastable, highly reactive O($^{1}D$) atoms. We examine the reactivity of these oxygen atoms generated by UV photolysis of O$_3$ with methyl cyanide (CH$_3$CN). These studies are conducted in an ultrahigh vacuum chamber at cryogenic and low-pressure conditions equipped with in situ infrared spectroscopy to monitor destruction and product formation in real time. We conclude that oxygen atoms rapidly insert into CH$_3$CN to produce primarily methyl isocyanate (CH$_3$NCO) in matrix free ices. Over the range from 10 K to 40 K, we observe no temperature dependence to either CH$_3$CN destruction or CH$_3$NCO production. When placing CH$_3$CN:O$_3$ in H$_2$O and CO$_2$ ice matrices, we find that CH$_3$NCO formation remains robust, but that the yield likely decreases due to competing reaction pathways. In the case of the H$_2$O ice we also observe a shift in product branching ratios towards alternative pathways such as the formation of hydroxyacetonitrile (HOCH$_2$CN). Overall, our results demonstrate that oxygen atom reactivity provides an important channel for generating chemical complexity from nitriles on cold grains where radical mobility is limited.

astro-ph.GA