CO2_2 Infrared Phonon Modes in Interstellar Ice Mixtures

CO$_2$ ice is an important reservoir of carbon and oxygen in star and planet forming regions. Together with water and CO, CO$_2$ sets the physical and chemical characteristics of interstellar icy grain mantles, including desorption and diffusion energies for other ice constituents. A detailed understanding of CO$_2$ ice spectroscopy is a prerequisite to characterize CO$_2$ interactions with other volatiles both in interstellar ices and in laboratory experiments of interstellar ice analogs. We report laboratory spectra of the CO$_2$ longitudinal optical (LO) phonon mode in pure CO$_2$ ice and in CO$_2$ ice mixtures with H$_2$O, CO, O$_2$ components. We show that the LO phonon mode position is sensitive to the mixing ratio of various ice components of astronomical interest. In the era of JWST, this characteristic could be used to constrain interstellar ice compositions and morphologies. More immediately, LO phonon mode spectroscopy provides a sensitive probe of ice mixing in the laboratory and should thus enable diffusion measurements with higher precision than has been previously possible

Evidence for Multiple Pathways to Deuterium Enhancements in Protoplanetary Disks

The distributions of deuterated molecules in protoplanetary disks are expected to depend on the molecular formation pathways. We use observations of spatially resolved DCN emission from the disk around TW Hya, acquired during ALMA Science verification with a ~3" synthesized beam, together with comparable DCO+ observations from the Submillimeter Array, to investigate differences in the radial distributions of these species and hence differences in their formation chemistry. In contrast to DCO+, which shows an increasing column density with radius, DCN is better fit by a model that is centrally peaked. We infer that DCN forms at a smaller radii and thus at higher temperatures than DCO+. This is consistent with chemical network model predictions of DCO+ formation from H2D+ at T<30 K and DCN formation from additional pathways involving CH2D+ at higher temperatures. We estimate a DCN/HCN abundance ratio of ~0.017, similar to the DCO+/HCO+ abundance ratio. Deuterium fractionation appears to be efficient at a range of temperatures in this protoplanetary disk. These results suggest caution in interpreting the range of deuterium fractions observed in Solar System bodies, as multiple formation pathways should be taken into account.Comment: accepted for publication in Ap

CO diffusion and desorption kinetics in CO2_2 ices

Diffusion of species in icy dust grain mantles is a fundamental process that shapes the chemistry of interstellar regions; yet measurements of diffusion in interstellar ice analogs are scarce. Here we present measurements of CO diffusion into CO$_2$ ice at low temperatures (T=11--23~K) using CO$_2$ longitudinal optical (LO) phonon modes to monitor the level of mixing of initially layered ices. We model the diffusion kinetics using Fick's second law and find the temperature dependent diffusion coefficients are well fit by an Arrhenius equation giving a diffusion barrier of 300 $\pm$ 40 K. The low barrier along with the diffusion kinetics through isotopically labeled layers suggest that CO diffuses through CO$_2$ along pore surfaces rather than through bulk diffusion. In complementary experiments, we measure the desorption energy of CO from CO$_2$ ices deposited at 11-50 K by temperature-programmed desorption (TPD) and find that the desorption barrier ranges from 1240 $\pm$ 90 K to 1410 $\pm$ 70 K depending on the CO$_2$ deposition temperature and resultant ice porosity. The measured CO-CO$_2$ desorption barriers demonstrate that CO binds equally well to CO$_2$ and H$_2$O ices when both are compact. The CO-CO$_2$ diffusion-desorption barrier ratio ranges from 0.21-0.24 dependent on the binding environment during diffusion. The diffusion-desorption ratio is consistent with the above hypothesis that the observed diffusion is a surface process and adds to previous experimental evidence on diffusion in water ice that suggests surface diffusion is important to the mobility of molecules within interstellar ices

SO and SiS Emission Tracing an Embedded Planet and Compact 12^{12}CO and 13^{13}CO Counterparts in the HD 169142 Disk

Planets form in dusty, gas-rich disks around young stars, while at the same time, the planet formation process alters the physical and chemical structure of the disk itself. Embedded planets will locally heat the disk and sublimate volatile-rich ices, or in extreme cases, result in shocks that sputter heavy atoms such as Si from dust grains. This should cause chemical asymmetries detectable in molecular gas observations. Using high-angular-resolution ALMA archival data of the HD 169142 disk, we identify compact SO J=8$_8$-7$_7$ and SiS J=19-18 emission coincident with the position of a ${\sim}$2 M$_{\rm{Jup}}$ planet seen as a localized, Keplerian NIR feature within a gas-depleted, annular dust gap at ${\approx}$38 au. The SiS emission is located along an azimuthal arc and has a similar morphology as a known $^{12}$CO kinematic excess. This is the first tentative detection of SiS emission in a protoplanetary disk and suggests that the planet is driving sufficiently strong shocks to produce gas-phase SiS. We also report the discovery of compact $^{12}$CO and $^{13}$CO J=3-2 emission coincident with the planet location. Taken together, a planet-driven outflow provides the best explanation for the properties of the observed chemical asymmetries. We also resolve a bright, azimuthally-asymmetric SO ring at ${\approx}$24 au. While most of this SO emission originates from ice sublimation, its asymmetric distribution implies azimuthal temperature variations driven by a misaligned inner disk or planet-disk interactions. Overall, the HD 169142 disk shows several distinct chemical signatures related to giant planet formation and presents a powerful template for future searches of planet-related chemical asymmetries in protoplanetary disks.Comment: 22 pages, 12 figures, accepted for publication in ApJ

The ancient heritage of water ice in the solar system

Identifying the source of Earth's water is central to understanding the origins of life-fostering environments and to assessing the prevalence of such environments in space. Water throughout the solar system exhibits deuterium-to-hydrogen enrichments, a fossil relic of low-temperature, ion-derived chemistry within either (i) the parent molecular cloud or (ii) the solar nebula protoplanetary disk. Utilizing a comprehensive treatment of disk ionization, we find that ion-driven deuterium pathways are inefficient, curtailing the disk's deuterated water formation and its viability as the sole source for the solar system's water. This finding implies that if the solar system's formation was typical, abundant interstellar ices are available to all nascent planetary systems.Comment: 33 pages, 7 figures including main text and supplementary materials. Published in Scienc

Exploring the Origins of Deuterium Enrichments in Solar Nebular Organics

Deuterium-to-hydrogen (D/H) enrichments in molecular species provide clues about their original formation environment. The organic materials in primitive solar system bodies have generally higher D/H ratios and show greater D/H variation when compared to D/H in solar system water. We propose this difference arises at least in part due to 1) the availability of additional chemical fractionation pathways for organics beyond that for water, and 2) the higher volatility of key carbon reservoirs compared to oxygen. We test this hypothesis using detailed disk models, including a sophisticated, new disk ionization treatment with a low cosmic ray ionization rate, and find that disk chemistry leads to higher deuterium enrichment in organics compared to water, helped especially by fractionation via the precursors CH$_2$D$^+$/CH$_3^+$. We also find that the D/H ratio in individual species varies significantly depending on their particular formation pathways. For example, from $\sim20-40$ AU, CH$_4$ can reach $\rm{D/H\sim2\times10^{-3}}$, while D/H in CH$_3$OH remains locally unaltered. Finally, while the global organic D/H in our models can reproduce intermediately elevated D/H in the bulk hydrocarbon reservoir, our models are unable to reproduce the most deuterium-enriched organic materials in the solar system, and thus our model requires some inheritance from the cold interstellar medium from which the Sun formed.Comment: 11 pages, 7 figures, accepted for publication in Ap