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Register a new userMethanol formation via oxygen insertion chemistry in ice
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We present experimental constraints on the insertion of oxygen atoms into methane to form methanol in astrophysical ice analogs. In gas-phase and theoretical studies this process has previously been demonstrated to have a very low or non-existent energy barrier, but the energetics and mechanisms have not yet been characterized in the solid state. We use a deuterium UV lamp filtered by a sapphire window to selectively dissociate O2 within a mixture of O2:CH4 and observe efficient production of CH3OH via O(1D) insertion. CH3OH growth curves are fit with a kinetic model, and we observe no temperature dependence of the reaction rate constant at temperatures below the oxygen desorption temperature of 25K. Through an analysis of side products we determine the branching ratio of ice-phase oxygen insertion into CH4: ~65% of insertions lead to CH3OH with the remainder leading instead to H2CO formation. There is no evidence for CH3 or OH radical formation, indicating that the fragmentation is not an important channel and that insertions typically lead to increased chemical complexity. CH3OH formation from O2 and CH4 diluted in a CO-dominated ice similarly shows no temperature dependence, consistent with expectations that insertion proceeds with a small or non-existent barrier. Oxygen insertion chemistry in ices should therefore be efficient under low-temperature ISM-like conditions, and could provide an important channel to complex organic molecule formation on grain surfaces in cold interstellar regions such as cloud cores and protoplanetary disk midplanes.
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Molecular oxygen has been detected in the coma of comet 67P/Churyumov--Gerasimenko with a mean abundance of 3.80 $pm$ 0.85% by the ROSINA mass spectrometer on board the Rosetta spacecraft. To account for the presence of this species in comet 67P/Churyumov--Gerasimenko, it has been shown that the radiolysis of ice grains precursors of comets is a viable mechanism in low-density environments, such as molecular clouds. Here, we investigate the alternative possibility that the icy grains present in the midplane of the protosolar nebula were irradiated during their vertical transport between the midplane and the upper layers over a large number of cycles, as a result of turbulent mixing. Consequently, these grains spent a non-negligible fraction of their lifetime in the disks upper regions, where the irradiation by cosmic rays was strong. To do so, we used a coupled disk-transport-irradiation model to calculate the time evolution of the molecular oxygen abundance radiolytically produced in ice grains. Our computations show that, even if a significant fraction of the icy particles have followed a back and forth cycle towards the upper layers of the disk over 10 million of years, a timespan far exceeding the formation timescale of comet 67P/Churyumov--Gerasimenko, the amount of produced molecular oxygen is at least two orders of magnitude lower than the Rosetta observations. We conclude that the most likely scenario remains the formation of molecular oxygen in low-density environments, such as the presolar cloud, prior to the genesis of the protosolar nebula.
Gas-phase methanol was recently detected in a protoplanetary disk for the first time with ALMA. The peak abundance and distribution of methanol observed in TW Hya differed from that predicted by chemical models. Here, the chemistry of methanol gas and ice is calculated using a physical model tailored for TW Hya with the aim to contrast the results with the recent detection in this source. New pathways for the formation of larger complex molecules (e.g., ethylene glycol) are included in an updated chemical model, as well as the fragmentation of methanol ice upon photodesorption. It is found that including fragmentation upon photodesorption improves the agreement between the peak abundance reached in the chemical models with that observed in TW Hya ($sim 10^{-11}$ with respect to ce{H2}); however, the model predicts that the peak in emission resides a factor of $2-3$ farther out in the disk than the ALMA images. Reasons for the persistent differences in the gas-phase methanol distribution between models and the observations of TW Hya are discussed. These include the location of the ice reservoir which may coincide with the compact mm-dust disk ($lesssim 60$~au) and sources of gas-phase methanol which have not yet been considered in models. The possibility of detecting larger molecules with ALMA is also explored. Calculations of the rotational spectra of complex molecules other than methanol using a parametric model constrained by the TW Hya observations suggest that the detection of individual emission lines of complex molecules with ALMA remains challenging. However, the signal-to-noise ratio can be enhanced via stacking of multiple transitions which have similar upper energy levels.
We present spectroscopic observations of a sample of 15 embedded young stellar objects (YSOs) in the Large Magellanic Cloud (LMC). These observations were obtained with the Spitzer Infrared Spectrograph (IRS) as part of the SAGE-Spec Legacy program. We analyze the two prominent ice bands in the IRS spectral range: the bending mode of CO_2 ice at 15.2 micron and the ice band between 5 and 7 micron that includes contributions from the bending mode of water ice at 6 micron amongst other ice species. The 5-7 micron band is difficult to identify in our LMC sample due to the conspicuous presence of PAH emission superimposed onto the ice spectra. We identify water ice in the spectra of two sources; the spectrum of one of those sources also exhibits the 6.8 micron ice feature attributed to ammonium and methanol. We model the CO_2 band in detail, using the combination of laboratory ice profiles available in the literature. We find that a significant fraction (> 50%) of CO_2 ice is locked in a water-rich component, consistent with what is observed for Galactic sources. The majority of the sources in the LMC also require a pure-CO_2 contribution to the ice profile, evidence of thermal processing. There is a suggestion that CO_2 production might be enhanced in the LMC, but the size of the available sample precludes firmer conclusions. We place our results in the context of the star formation environment in the LMC.
Methanol and complex organic molecules have been found in cold starless cores, where a standard warm-up scenario would not work because of the absence of heat sources. A recent chemical model attributed the presence of methanol and large organics to the efficient chemical desorption and a class of neutral-neutral reactions that proceed fast at low temperatures in the gas phase. The model calls for a high abundance of methanol ice at the edge of the CO freeze-out zone in cold cloud cores. We performed medium resolution spectroscopy toward 3 field stars behind the starless core L1544 at 3 $mu$m to constrain the methanol ice abundance and compare it with the model predictions. One of the field stars shows a methanol-ice abundance of 11% with respect to water ice. This is higher than the typical methanol abundance previously found in cold cloud cores (4%), but is 4.5 times smaller than predicted. The reason for the disagreement between the observations and the model calculations is not yet understood.
One of the primary mechanisms for inferring the dynamical history of planets in our Solar System and in exoplanetary systems is through observation of elemental ratios (i.e. C/O). The ability to effectively use these observations relies critically on a robust understanding of the chemistry and evolutionary history of the observed abundances. Significant efforts have been devoted to this area from within astrochemistry circles, and these efforts should be supported going forward by the larger exoplanetary science community. In addition, the construction of a next-generation radio interferometer will be required to test many of these predictive models in situ, while simultaneously providing the resolution necessary to pinpoint the location of planets in formation.
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