Detection of N2_2D+^+ in a protoplanetary disk

Observations of deuterium fractionation in the solar system, and in interstellar and circumstellar material, are commonly used to constrain the formation environment of volatiles. Toward protoplanetary disks, this approach has been limited by the small number of detected deuterated molecules, i.e. DCO$^+$ and DCN. Based on ALMA Cycle 2 observations toward the disk around the T Tauri star AS 209, we report the first detection of N$_2$D$^+$ (J=3-2) in a protoplanetary disk. These data are used together with previous Submillimeter Array observations of N$_2$H$^+$ (J=3-2) to estimate a disk-averaged D/H ratio of 0.3--0.5, an order of magnitude higher than disk-averaged ratios previously derived for DCN/HCN and DCO$^+$/HCO$^+$ around other young stars. The high fractionation in N$_2$H$^+$ is consistent with model predictions. The presence of abundant N$_2$D$^+$ toward AS 209 also suggests that N$_2$D$^+$ and the N$_2$D$^+$/N$_2$H$^+$ ratio can be developed into effective probes of deuterium chemistry, kinematics, and ionization processes outside the CO snowline of disks.Comment: 5 pages, 3 figures, accepted by ApJ

H2CO and N2H+ in Protoplanetary Disks: Evidence for a CO-ice Regulated Chemistry

We present Submillimeter Array observations of H2CO and N2H+ emission in the disks around the T Tauri star TW Hya and the Herbig Ae star HD 163296 at 2"-6" resolution and discuss the distribution of these species with respect to CO freeze-out. The H2CO and N2H+ emission toward HD 163296 does not peak at the continuum emission center that marks the stellar position but is instead significantly offset. Using a previously developed model for the physical structure of this disk, we show that the H2CO observations are reproduced if H2CO is present predominantly in the cold outer disk regions. A model where H2CO is present only beyond the CO snow line (estimated at a radius of 160 AU) matches the observations well. We also show that the average H2CO excitation temperature, calculated from two transitions of H2CO observed in these two disks and a larger sample of disks around T Tauri stars in the DISCS (the Disk Imaging Survey of Chemistry with SMA) program, is consistent with the CO freeze-out temperature of 20 K. In addition, we show that N2H+ and H2CO line fluxes in disks are strongly correlated, indicative of co-formation of these species across the sample. Taken together, these results imply that H2CO and N2H+ are generally present in disks only at low temperatures where CO depletes onto grains, consistent with fast destruction of N2H+ by gas-phase CO, and in situ formation of H2CO through hydrogenation of CO ice. In this scenario H2CO, CH3OH and N2H+ emission in disks should appear as rings with the inner edge at the CO midplane snow line. This prediction can be tested directly using observations from ALMA with higher resolution and better sensitivity.Comment: 39 pages, 12 figures, 3 tables, accepted for publication in Ap

Complex organic molecules during low-mass star formation: Pilot survey results

Complex organic molecules (COMs) are known to be abundant toward some low-mass young stellar objects (YSOs), but how these detections relate to typical COM abundance are not yet understood. We aim to constrain the frequency distribution of COMs during low-mass star formation, beginning with this pilot survey of COM lines toward six embedded YSOs using the IRAM 30m telescope. The sample was selected from the Spitzer c2d ice sample and covers a range of ice abundances. We detect multiple COMs, including CH3CN, toward two of the YSOs, and tentatively toward a third. Abundances with respect to CH3OH vary between 0.7 and 10%. This sample is combined with previous COM observations and upper limits to obtain a frequency distributions of CH3CN, HCOOCH3, CH3OCH3 and CH3CHO. We find that for all molecules more than 50% of the sample have detections or upper limits of 1-10% with respect to CH3OH. Moderate abundances of COMs thus appear common during the early stages of low-mass star formation. A larger sample is required, however, to quantify the COM distributions, as well as to constrain the origins of observed variations across the sample.Comment: 11 pages, 8 figures, accepted for publication in Ap

Oxygen atom reactions with C2H6, C2H4, and C2H2 in ices

Oxygen atom addition and insertion reactions may provide a pathway to chemical complexity in ices that are too cold for radicals to diffuse and react. We have studied the ice-phase reactions of photo-produced oxygen atoms with C2 hydrocarbons under ISM-like conditions. The main products of oxygen atom reactions with ethane are ethanol and acetaldehyde; with ethylene are ethylene oxide and acetaldehyde; and with acetylene is ketene. The derived branching ratio from ethane to ethanol is ~0.74 and from ethylene to ethylene oxide is ~0.47. For all three hydrocarbons there is evidence of an effectively barrierless reaction with O(^1D) to form oxygen-bearing organic products; in the case of ethylene, there may be an additional barriered contribution of the ground-state O(^3P) atom. Thus, oxygen atom reactions with saturated and unsaturated hydrocarbons are a promising pathway to chemical complexity even at very low temperatures where the diffusion of radical species is thermally inaccessible.Comment: 20 pages, 16 figures. Accepted for publication in Ap

Methanol formation via oxygen insertion chemistry in ice

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

Evidence for a CO desorption front in the outer AS 209 disk

Millimeter observations of CO isotopologues are often used to make inferences about protoplanetary disk gas density and temperature structures. The accuracy of these estimates depends on our understanding of CO freezeout and desorption from dust grains. Most models of these processes indicate that CO column density decreases monotonically with distance from the central star due to a decrease in gas density and freezeout beyond the CO snowline. We present ALMA Cycle 2 observations of $^{12}$CO, $^{13}$CO, and C$^{18}$O $J=2-1$ emission that instead suggest CO enhancement in the outer disk of T Tauri star AS 209. Most notably, the C$^{18}$O emission consists of a central peak and a ring at a radius of $\sim1''$ (120 AU), well outside the expected CO snowline. We propose that the ring arises from the onset of CO desorption near the edge of the millimeter dust disk. CO desorption exterior to a CO snowline may occur via non-thermal processes involving cosmic rays or high-energy photons, or via a radial thermal inversion arising from dust migration.Comment: 8 pages, 4 figures, published in ApJ

Science with an ngVLA: Organics in Disk Midplanes with the ngVLA

Planets assemble in the midplanes of protoplanetary disks. The compositions of dust and gas in the disk midplane region determine the compositions of nascent planets, including their chemical hospitality to life. In this context, the distributions of volatile organic material across the planet and comet forming zones is of special interest. These are difficult to access in the disk midplane at IR and even millimeter wavelengths due to dust opacity, which can veil the midplane, low intrinsic molecular abundances due to efficient freeze-out, and, in the case of mid-sized organics, a mismatch between expected excitation temperatures and accessible line upper energy levels. At ngVLA wavelengths, the dust is optically thin, enabling observations into the planet forming disk midplane. ngVLA also has the requisite sensitivity. Using TW Hya as a case study, we show that ngVLA will be able to map out the distributions of diagnostic organics, such as CH3CN, in nearby protoplanetary disks.Comment: To be published in the ASP Monograph Series, 'Science with a Next-Generation VLA', ed. E. J. Murphy (ASP, San Francisco, CA

Carbon Chains and Methanol toward Embedded Protostars

Large interstellar organic molecules are potential precursors of prebiotic molecules. Their formation pathways and chemical relationships with one another and simpler molecules are therefore of great interest. In this paper, we address the relationship between two classes of large organic molecules, carbon chains and saturated complex organic molecules (COMs), at the early stages of star formation through observations of C4H and CH3OH. We surveyed these molecules with the IRAM 30m telescope toward 16 deeply embedded low-mass protostars selected from the Spitzer c2d ice survey. We find that CH3OH and C4H are positively correlated indicating that these two classes of molecules can coexist during the embedded protostellar stage. The C4H/CH3OH gas abundance ratio tentatively correlates with the CH4/CH3OH ice abundance ratio in the same lines of sight. This relationship supports a scenario where carbon chain formation in protostellar envelopes begins with CH4 ice desorption.Comment: Accepted for publication by ApJ, 10 Pages, 7 Figures, 4 Table

Carbon Chain Molecules Toward Embedded Low-Mass Protostars

Carbon chain molecules may be an important reservoir of reactive organics during star and planet formation. Carbon chains have been observed toward several low-mass young stellar objects (YSOs), but their typical abundances and chemical relationships in such sources are largely unconstrained. We present a carbon chain survey toward 16 deeply embedded (Class 0/I) low-mass protostars made with the IRAM 30 m telescope. Carbon chains are found to be common at this stage of protostellar evolution. We detect CCS, CCCS, HC$_3$N, HC$_5$N, l-C$_3$H, and C$_4$H toward 88%, 38%, 75%, 31%, 81%, and 88% of sources, respectively. Derived column densities for each molecule vary by one to two orders of magnitude across the sample. As derived from survival analysis, median column densities range between 1.2$\times 10^{11}$ cm$^{-2}$ (CCCS) and 1.5$\times 10^{13}$ cm$^{-2}$ (C$_4$H) and estimated fractional abundances with respect to hydrogen range between 2$\times 10^{-13}$ (CCCS) and 5$\times 10^{-11}$ (C$_4$H), which are low compared to cold cloud cores, warm carbon chain chemistry (WCCC) sources, and protostellar model predictions. We find significant correlations between molecules of the same carbon chain families, as well as between the cyanpolyynes (HC$_{\rm n}$N) and the pure hydrocarbon chains (C$_{\rm n}$H). This latter correlation is explained by a closely-related production chemistry of C$_{\rm{n}}$H and cyanpolyynes during low-mass star formation.Comment: 31 pages, 14 figures, accepted for publication in Ap

The Ionization Fraction in the DM Tau Protoplanetary Disk

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=1_10 - 1_11, 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 NH2D+ < 4 - 21 \times 1012 cm-2. We adopt a parametric model for the disk structure from the literature and use new IRAM 30 meter 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 lines 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 \simeq 4 \times 10-10, (2) a cooler molecular layer with T = 16-20 K where N2H+ and DCO+ abundances are predicted to peak, with xi \simeq 3\times10-11, and (3) the cold, dense midplane with T<16 K where H3+ and its deuterated isotopologues are the main carriers of positive charge, with xi < 3\times10-10. 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+ 1_10 - 1_11 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.Comment: Accepted for publication in ApJ. 20 pages, including 5 figure