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Theoretical models and observations suggest that the abundances of molecular ions in protoplanetary disks should be highly sensitive to the variable ionization conditions set by the young central star. We present a search for temporal flux variability of HCO+ J = 1–0, which was observed as a part of the Molecules with Atacama Large Millimeter/submillimeter Array (ALMA) at Planet-forming Scales ALMA Large Program. We split out and imaged the line and continuum data for each individual day the five sources were observed (HD 163296, AS 209, GM Aur, MWC 480, and IM Lup, with between three and six unique visits per source). Significant enhancement (>3 σ) was not observed, but we find variations in the spectral profiles in all five disks. Variations in AS 209, GM Aur, and HD 163296 are tentatively attributed to variations in HCO+ flux, while variations in IM Lup and MWC 480 are most likely introduced by differences in the uv coverage, which impact the amount of recovered flux during imaging. The tentative detections and low degree of variability are consistent with expectations of X-ray flare-driven HCO+ variability, which requires relatively large flares to enhance the HCO+ rotational emission at significant (>20%) levels. These findings also demonstrate the need for dedicated monitoring campaigns with high signal-to-noise ratios to fully characterize X-ray flare-driven chemistry. [ABSTRACT FROM AUTHOR]

Planets and planetesimals acquire their volatiles through ice and gas accretion in protoplanetary disks. In these disks, the division of volatile molecules between the condensed and gaseous phases determines the quantity of volatiles accreted by planets in different regions of the disk. This division can be strongly affected by entrapment of volatiles into less volatile ice matrices, resulting in different radial profiles of common volatiles and elemental ratios than would otherwise be expected. In this study we use laboratory experiments to explore the ability of abundant interstellar and cometary ice matrices, i.e., H2O and CO2, to trap the hypervolatiles 13CO, 12CH4, 15N2, and Ar. We measure entrapment efficiencies through temperature programmed desorption for two ice thicknesses (10 and 50 monolayers) and two mixing ratios (3:1 and 10:1) for each matrix:volatile combination. We find that ice entrapment efficiencies increase with ice thickness and ice mixing ratio to a maximum of ∼65% for all hypervolatiles. Entrapment efficiencies are comparable for all hypervolatiles, and for the two ice matrices. We further find that the entrapment efficiency is relatively insensitive to the ice deposition temperature between 10 and 30 K with the possible exception of CH4 in CO2 ice. Together these results suggest that hypervolatile entrapment at low temperatures (<30 K) is a remarkably robust and species-independent process. [ABSTRACT FROM AUTHOR]

Planets form in disks of gas and dust around young stars. The disk molecular reservoirs and their chemical evolution affect all aspects of planet formation, from the coagulation of dust grains into pebbles to the elemental and molecular compositions of the mature planet. Disk chemistry also enables unique probes of disk structures and dynamics, including those directly linked to ongoing planet formation. We review the protoplanetary disk chemistry of the volatile elements H, O, C, N, S, and P; the associated observational and theoretical methods; and the links between disk and planet chemical compositions. Three takeaways from this review are: The disk chemical composition, including the organic reservoirs, is set by both inheritance and in situ chemistry. Disk gas and solid O/C/N/H elemental ratios often deviate from stellar values due to a combination of condensation of molecular carriers, chemistry, and dynamics. Chemical, physical, and dynamical processes in disks are closely linked, which complicates disk chemistry modeling, but these links also present an opportunity to develop chemical probes of different aspects of disk evolution and planet formation. [ABSTRACT FROM AUTHOR]

To date, at least three comets—2I/Borisov, C/2016 R2 (PanSTARRS), and C/2009 P1 (Garradd)—have been observed to have unusually high CO concentrations compared to water. We attempt to explain these observations by modeling the effect of drifting solid (ice and dust) material on the ice compositions in protoplanetary disks. We find that, independent of the exact disk model parameters, we always obtain a region of enhanced ice-phase CO/H2O that spreads out in radius over time. The inner edge of this feature coincides with the CO snowline. Almost every model achieves at least CO/H2O of unity, and one model reaches a CO/H2O ratio >10. After running our simulations for 1 Myr, an average of 40% of the disk ice mass contains more CO than H2O ice. In light of this, a population of CO-ice-enhanced planetesimals are likely to generally form in the outer regions of disks, and we speculate that the aforementioned CO-rich comets may be more common, both in our own solar system and in extrasolar systems, than previously expected. [ABSTRACT FROM AUTHOR]

M-stars are the most common hosts of planetary systems in the Galaxy. Protoplanetary disks around M-stars thus offer a prime opportunity to study the chemistry of planet-forming environments. We present an Atacama Large Millimeter/submillimeter Array survey of molecular line emission toward a sample of five protoplanetary disks around M4–M5 stars (FP Tau, J0432+1827, J1100-7619, J1545-3417, and Sz 69). These observations can resolve chemical structures down to tens of astronomical units. Molecular lines of 12CO, 13CO, C18O, C2H, and HCN are detected toward all five disks. Lines of H2CO and DCN are detected toward 2/5 and 1/5 disks, respectively. For disks with resolved C18O, C2H, HCN, and H2CO emission, we observe substructures similar to those previously found in disks around solar-type stars (e.g., rings, holes, and plateaus). C2H and HCN excitation conditions estimated interior to the pebble disk edge for the bright disk J1100-7619 are consistent with previous measurements around solar-type stars. The correlation previously found between C2H and HCN fluxes for solar-type disks extends to our M4–M5 disk sample, but the typical C2H/HCN ratio is higher for the M4–M5 disk sample. This latter finding is reminiscent of the hydrocarbon enhancements found by previous observational infrared surveys in the innermost (<10 au) regions of M-star disks, which is intriguing since our disk-averaged fluxes are heavily influenced by flux levels in the outermost disk, exterior to the pebble disk edge. Overall, most of the observable chemistry at 10–100 au appears similar for solar-type and M4–M5 disks, but hydrocarbons may be more abundant around the cooler stars. [ABSTRACT FROM AUTHOR]

Connecting the composition of planet-forming disks with that of gas giant exoplanet atmospheres, in particular through C/O ratios, is one of the key goals of disk chemistry. Small hydrocarbons like C2H and C3H2 have been identified as tracers of C/O, as they form abundantly under high C/O conditions. We present resolved c–C3H2 observations from the TW Hya Rosetta Stone Project, a program designed to map the chemistry of common molecules at 15–20 au resolution in the TW Hya disk. Augmented by archival data, these observations comprise the most extensive multi-line set for disks of both ortho and para spin isomers spanning a wide range of energies, Eu = 29–97 K. We find the ortho-to-para ratio of c–C3H2 is consistent with 3 throughout extent of the emission, and the total abundance of both c–C3H2 isomers is (7.5–10) × 10−11 per H atom, or 1%–10% of the previously published C2H abundance in the same source. We find c–C3H2 comes from a layer near the surface that extends no deeper than z/r = 0.25. Our observations are consistent with substantial radial variation in gas-phase C/O in TW Hya, with a sharp increase outside ∼30 au. Even if we are not directly tracing the midplane, if planets accrete from the surface via, e.g., meridional flows, then such a change should be imprinted on forming planets. Perhaps interestingly, the HR 8799 planetary system also shows an increasing gradient in its giant planets' atmospheric C/O ratios. While these stars are quite different, hydrocarbon rings in disks are common, and therefore our results are consistent with the young planets of HR 8799 still bearing the imprint of their parent disk's volatile chemistry. [ABSTRACT FROM AUTHOR]

Planets form and obtain their compositions in disks of gas and dust around young stars. The chemical compositions of these planet-forming disks regulate all aspects of planetary compositions from bulk elemental inventories to access to water and reactive organics, i.e. a planet's hospitality to life and its chemical origins. Disk chemical structures are in their turn governed by a combination of in situ chemical processes, and inheritance of molecules from the preceding evolutionary stages of the star formation process. In this review we present our current understanding of the chemical processes active in pre- and protostellar environments that set the initial conditions for disks, and the disk chemical processes that evolve the chemical conditions during the first million years of planet formation. We review recent observational, laboratory and theoretical discoveries that have led to the present view of the chemical environment within which planets form, and their effects on the compositions of nascent planetary systems. We also discuss the many unknowns that remain and outline some possible pathways to addressing them. [ABSTRACT FROM AUTHOR]

Formaldehyde (H2CO) is an important precursor to organics like methanol (CH3OH). It is important to understand the conditions that produce H2CO and prebiotic molecules during star and planet formation. H2CO possesses both gas-phase and solid-state formation pathways, involving either UV-produced radical precursors or CO ice and cold (≲20 K) dust grains. To understand which pathway dominates, gaseous H2CO's ortho-to-para ratio (OPR) has been used as a probe, with a value of 3 indicating "warm" conditions and <3 linked to cold formation in the solid state. We present spatially resolved Atacama Large Millimeter/submillimeter Array observations of multiple ortho- and para-H2CO transitions in the TW Hya protoplanetary disk to test H2CO formation theories during planet formation. We find disk-averaged rotational temperatures and column densities of 33 ± 2 K, (1.1 ± 0.1) × 1012 cm−2 and 25 ± 2 K, (4.4 ± 0.3) × 1011 cm−2 for ortho- and para-H2CO, respectively, and an OPR of 2.49 ± 0.23. A radially resolved analysis shows that the observed H2CO emits mostly at rotational temperatures of 30–40 K, corresponding to a layer with z/R ≥ 0.25. The OPR is consistent with 3 within 60 au, the extent of the pebble disk, and decreases beyond 60 au to 2.0 ± 0.5. The latter corresponds to a spin temperature of 12 K, well below the rotational temperature. The combination of relatively uniform emitting conditions, a radial gradient in the OPR, and recent laboratory experiments and theory on OPR ratios after sublimation, led us to speculate that gas-phase formation is responsible for the observed H2CO across the TW Hya disk. [ABSTRACT FROM AUTHOR]

The volatile composition of a planet is determined by the inventory of gas and ice in the parent disk. The volatile chemistry in the disk is expected to evolve over time, though this evolution is poorly constrained observationally. We present Atacama Large Millimeter/submillimeter Array observations of C18O, C2H, and the isotopologues H13CN, HC15N, and DCN toward five Class 0/I disk candidates. Combined with a sample of 14 Class II disks presented in Bergner et al., this data set offers a view of volatile chemical evolution over the disk lifetime. Our estimates of C18O abundances are consistent with a rapid depletion of CO in the first ∼0.5–1 Myr of the disk lifetime. We do not see evidence that C2H and HCN formation are enhanced by CO depletion, possibly because the gas is already quite under-abundant in CO. Further CO depletion may actually hinder their production by limiting the gas-phase carbon supply. The embedded sources show several chemical differences compared to the Class II stage, which seem to arise from shielding of radiation by the envelope (impacting C2H formation and HC15N fractionation) and sublimation of ices from infalling material (impacting HCN and C18O abundances). Such chemical differences between Class 0/I and Class II sources may affect the volatile composition of planet-forming material at different stages in the disk lifetime. [ABSTRACT FROM AUTHOR]

There is mounting evidence that the composition and structure of planetary systems are intimately linked to their birth environments. During the past decade, several spectral surveys probed the chemistry of the earliest stages of star formation and late planet-forming disks. However, very little is known about the chemistry of intermediate protostellar stages, i.e., class I young stellar objects (YSOs), where planet formation may have already begun. We present here the first results of a 3 mm spectral survey performed with the IRAM 30 m telescope to investigate the chemistry of a sample of seven class I YSOs located in the Taurus star-forming region. These sources were selected to embrace the wide diversity identified for low-mass protostellar envelope and disk systems. We present detections and upper limits of 13 small (Natoms ≤ 3) C, N, O, and S carriers—namely, CO, HCO+, HCN, HNC, CN, N2H+, C2H, CS, SO, HCS+, C2S, SO2, and OCS—and some of their D, 13C, 15N, 18O, 17O, and 34S isotopologues. Together, these species provide constraints on gas-phase C/N/O ratios, D and 15N fractionation, source temperature, and UV exposure, as well as the overall S chemistry. We find substantial evidence of chemical differentiation among our source sample, some of which can be traced back to class I physical parameters, such as the disk-to-envelope mass ratio (proxy for class I evolutionary stage), source luminosity, and UV field strength. Overall, these first results allow us to start investigating the astrochemistry of class I objects; however, interferometric observations are needed to differentiate envelope versus disk chemistry. [ABSTRACT FROM AUTHOR]

While protoplanetary disks often appear to be compact and well organized in millimeter continuum emission, CO spectral line observations are increasingly revealing complex behavior at large distances from the host star. We present deep Atacama Large Millimeter/submillimeter Array maps of the J = 2−1 transition of 12CO, 13CO, and C18O, as well as the J = 3−2 transition of DCO+, toward the T Tauri star RU Lup at a resolution of ∼0.3″ (∼50 au). The CO isotopologue emission traces four major components of the RU Lup system: a compact Keplerian disk with a radius of ∼120 au, a non-Keplerian "envelope-like" structure surrounding the disk and extending to ∼260 au from the star, at least five blueshifted spiral arms stretching up to 1000 au, and clumps outside the spiral arms located up to 1500 au in projection from RU Lup. We comment on potential explanations for RU Lup's peculiar gas morphology, including gravitational instability, accretion of material onto the disk, or perturbation by another star. RU Lup's extended non-Keplerian CO emission, elevated stellar accretion rate, and unusual photometric variability suggest that it could be a scaled-down Class II analog of the outbursting FU Ori systems. [ABSTRACT FROM AUTHOR]

The volatile contents of protoplanetary disks both set the potential for planetary chemistry and provide valuable probes of defining disk system characteristics such as stellar mass, gas mass, ionization, and temperature structure. Current disk molecular inventories are fragmented, however, giving an incomplete picture: unbiased spectral line surveys are needed to assess the volatile content. We present here an overview of such a survey of the protoplanetary disks around the Herbig Ae star MWC 480 and the T Tauri star LkCa 15 in ALMA Band 7, spanning ∼36 GHz from 275 to 317 GHz and representing an order of magnitude increase in sensitivity over previous single-dish surveys. We detect 14 molecular species (including isotopologues), with five species (C34S, 13CS, H2CS, DNC, and C2D) detected for the first time in protoplanetary disks. Significant differences are observed in the molecular inventories of MWC 480 and LkCa 15, and we discuss how these results may be interpreted in light of the different physical conditions of these two disk systems. [ABSTRACT FROM AUTHOR]

The gas and dust rich disks around young stars are the formation sites of planets. Observations of molecular trace species have great potential as probes of the disk structures and volatile compositions that together regulate planet formation. The disk around young star TW Hya has become a template for disk molecular studies due to a combination of proximity, a simple face-on geometry and richness in volatiles. It is unclear, however, how typical the chemistry of the TW disk is. In this proceeding, we review lessons learnt from exploring the TW Hya disk chemistry, focusing on the CO snowline, and on deuterium fractionation chemistry. We compare these results with new ALMA observations toward more distant, younger disks. We find that while all disks have some chemical structures in common, there are also substantial differences between the disks, which may be due to different initial conditions, structural or chemical evolutionary stages, or a combination of all three. [ABSTRACT FROM AUTHOR]

The distributions of deuterated molecules in protoplanetary disks are expected to depend on themolecular 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. [ABSTRACT FROM AUTHOR]

We present high-resolution (0".3 = 16 AU), high signal-to-noise ratio Submillimeter Array observations of the 870 µm (345 GHz) continuum and CO J = 3 - 2 line emission from the protoplanetary disk around TW Hya. Using continuum and line radiative transfer calculations, these data and the multiwavelength spectral energy distribution are analyzed together in the context of simple two-dimensional parametric disk structure models. Under the assumptions of a radially invariant dust population and gas-to-dust mass ratio, we are unable to simultaneously reproduce the CO and dust observations with model structures that employ either a single, distinct outer boundary or a smooth (exponential) taper at large radii. Instead, we find that the distribution of millimeter-sized dust grains in the TW Hya disk has a relatively sharp edge near 60 AU, contrary to the CO emission (and optical/infrared scattered light) that extends to a much larger radius of at least 215 AU. We discuss some possible explanations for the observed radial distribution of millimeter-sized dust grains and the apparent CO-dust size discrepancy, and suggest that they may be hallmarks of substructure in the dust disk or natural signatures of the growth and radial drift of solids that might be expected for disks around older pre-main-sequence stars like TW Hya. [ABSTRACT FROM AUTHOR]

We present millimeter-wave observations of several molecular ions in the disk around the pre-main-sequence star DM Tau and use these to investigate the ionization fraction in different regions of the disk. New Submillimeter Array (SMA) observations of H2D+ J = 11.0-11.1, N2H+ J = 4-3, and CO J = 3-2 are presented. H2D+ and N2H+ are not detected and using the CO 3-2 disk size the observations result in an upper limit of <0.47 K km s-1 for both lines, a factor of 2.5 below previous single-dish H2D+ observations. Assuming LTE, a disk midplane temperature of 10-20 K and estimates of the H2D+ o/p ratio, the observed limit corresponds to Due to image rights restrictions, multiple line equation(s) cannot be graphically displayed. We adopt a parametric model for the disk structure from the literature and use new IRAM 30 m telescope observations of the H13CO+ J = 3-2 line and previously published SMA observations of the N2H+ J = 3-2, HCO+ J = 3-2, and DCO+ J = 3-2 tines to constrain the ionization fraction, xi, in three temperature regions in the disk where theoretical considerations suggest different ions should dominate: (1) a warm, upper layer with T >20 K where CO is in the gas phase and HCO+ is most abundant, where we estimate xi ≃ 4 x 10-10; (2) a cooler molecular layer with T = 16-20 K where N2H+ and DCO+ abundances are predicted to peak, with xi ≃ 3 x 10-11; and (3) the cold, dense midplane with T <16 K where Due to image rights restrictions, multiple line equation(s) cannot be graphically displayed and its deuterated isotopologues are the main carriers of positive charge, with xi < 3 x 10-10. While there are considerable uncertainties, these estimates are consistent with a decreasing ionization fraction into the deeper, colder, and denser disk layers. Stronger constraints on the ionization fraction in the disk midplane will require not only substantially more sensitive observations of the H2D+ 11.0-11.1 line, but also robust determinations of the o/p ratio, observations of D2H+, and stronger constraints on where N2 is present in the gas phase. [ABSTRACT FROM AUTHOR]

We report Submillimeter Array observations of CO (J = 2-1, 3-2, and 6-5) and its isotopologues (13CO J = 2-1, CO18J = 2-1, and C17OJ = 3-2) in the disk around the Herbig Ae star HD 163296 at ∼2″ (250 AU) resolution, and interpret these data in the framework of a model that constrains the radial and vertical location of the line emission regions. First, we develop a physically self-consistent accretion disk model with an exponentially tapered edge that matches the spectral energy distribution and spatially resolved millimeter dust continuum emission. Then, we refine the vertical structure of the model using wide range of excitation conditions sampled by the CO lines, in particular the rarely observed J = 6-5 transition. By fitting 13CO data in this structure, we further constrain the vertical distribution of CO to lie between a lower boundary below which CO freezes out onto dust grains (T ≲ 19 K) and an upper boundary above which CO can be photodissociated (the hydrogen column density from the disk surface is ≲1021 cm-2). The freezeout at 19 K leads to a significant drop in the gas-phase CO column density beyond a radius of ∼ 155 AU, a "CO snow line" that we directly resolve. By fitting the abundances of all CO isotopologues, we derive isotopic ratios of 12C/13C, 16O/18O, and 18O/17O that are consistent with quiescent interstellar gas-phase values. This detailed model of the HD 163296 disk demonstrates the potential of a staged, parametric technique for constructing unified gas and dust structure models and constraining the distribution of molecular abundances using resolved multi-transition, multi-isotope observations. [ABSTRACT FROM AUTHOR]

This is the second in a series of papers based on data from DISCS, a Submillimeter Array observing program aimed at spatially and spectrally resolving the chemical composition of 12 protoplanetary disks. We present data on six Southern sky sources-TM Lup, SAO 206462 (HD 135344b), HD 142527, AS 209, AS 205, and V4046 Sgr-which complement the six sources in the Taurus star-forming region reported previously. CO 2-1 and HCO+ 3-2 emission are detected and resolved in all disks and show velocity patterns consistent with Keplerian rotation. Where detected, the emission from DCO+ 3-2, N2H+ 3-2, H2CO 303 202 and 414 - 313, HCN 3-2, and CN 233/4/2 - 122/3/1 are also generally spatially resolved. The detection rates are highest toward the M and K stars, while the F star SAO 206462 has only weak CN and HCN emission, and H2CO alone is detected toward HD 142527. These findings together with the statistics from the previous Taurus disks support the hypothesis that high detection rates of many small molecules depend on the presence of a cold and protected disk midplane, which is less common around F and A stars compared to M and K stars. Disk-averaged variations in the proposed radiation tracer CN/HCN are found to be small, despite a two orders of magnitude range of spectral types and accretion rates. In contrast, the resolved images suggest that the CN/HCN emission ratio varies with disk radius in at least two of the systems. There are no clear observational differences in the disk chemistry between the classical/full T Tauri disks and transitional disks. Furthermore, the observed line emission does not depend on the measured accretion luminosities or the number of infrared lines detected, which suggests that the chemistry outside of 100 AU is not coupled to the physical processes that drive the chemistry in the innermost few AU. [ABSTRACT FROM AUTHOR]

We present an observational and theoretical study of the primary ionizing agents (cosmic rays (CRs) and X-rays) in the TW Hya protoplanetary disk. We use a set of resolved and unresolved observations of molecular ions and other molecular species, encompassing 11 lines total, in concert with a grid of disk chemistry models. The molecular ion constraints comprise new data from the Submillimeter Array on HCO+, acquired at unprecedented spatial resolution, and data from the literature, including ALMA observations of N2H+. We vary the model incident CR flux and stellar X-ray spectra and find that TW Hya's HCO+ and N2H+ emission are best-fit by a moderately hard X-ray spectra, as would be expected during the “flaring” state of the star, and a low CR ionization rate, ζCR ≲ 10–19 s–1. This low CR rate is the first indication of the presence of CR exclusion by winds and/or magnetic fields in an actively accreting T Tauri disk system. With this new constraint, our best-fit ionization structure predicts a low turbulence “dead-zone” extending from the inner edge of the disk out to 50-65 AU. This region coincides with an observed concentration of millimeter grains, and we propose that the inner region of TW Hya is a dust (and possibly planet) growth factory as predicted by previous theoretical work. [ABSTRACT FROM AUTHOR]

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. Using a comprehensive treatment of disk ionization, we find that ion-driven deuterium pathways are inefficient, which curtails 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. [ABSTRACT FROM AUTHOR]