Synthesis of urea on the surface of interstellar water ice clusters. A quantum chemical study

Urea is a prebiotic molecule that has been detected in few sources of the interstellar medium (ISM) and in Murchison meteorite. Being stable against ultraviolet radiation and high-energy electron bombardment, urea is expected to be present in interstellar ices. Theoretical and experimental studies suggest that isocyanic acid (HNCO) and formamide (NH$_2$CHO) are possible precursors of urea. However, uncertainties still exist regarding its formation routes. Previous computational works characterised urea formation in the gas phase or in presence of few water molecules by reaction of formamide with nitrogen-bearing species. In this work, we investigated the reaction of HNCO + NH$_3$ on an 18 water molecules ice cluster model mimicking interstellar ice mantles by means of quantum chemical computations. We characterised different mechanisms involving both closed-shell and open-shell species at B3LYP-D3(BJ)/ma-def2-TZVP level of theory, in which the radical-radical H$_2$NCO + NH$_2$ coupling has been found to be the most favourable one due to being almost barrierless. In this path, the presence of the icy surfaces is crucial for acting as reactant concentrators/suppliers, as well as third bodies able to dissipate the energy liberated during the urea formation.Comment: 12 pages, 7 figures. Accepted for pubication in Icaru

ALMA chemical survey of disk-outflow sources in Taurus (ALMA-DOT)

The chemical composition of planets is inherited from that of the natal protoplanetary disk at the time of planet formation. Increasing observational evidence suggests that planet formation occurs in less than 1−2 Myr. This motivates the need for spatially resolved spectral observations of young Class I disks, as carried out by the ALMA chemical survey of Disk-Outflow sources in Taurus (ALMA-DOT). In the context of ALMA-DOT, we observe the edge-on disk around the Class I source IRAS 04302+2247 (the butterfly star) in the 1.3 mm continuum and five molecular lines. We report the first tentative detection of methanol (CH3OH) in a Class I disk and resolve, for the first time, the vertical structure of a disk with multiple molecular tracers. The bulk of the emission in the CO 2−1, CS 5−4, and o–H2CO 31, 2 − 21, 1 lines originates from the warm molecular layer, with the line intensity peaking at increasing disk heights, z, for increasing radial distances, r. Molecular emission is vertically stratified, with CO observed at larger disk heights (aperture z/r ∼ 0.41−0.45) compared to both CS and H2CO, which are nearly cospatial (z/r ∼ 0.21−0.28). In the outer midplane, the line emission decreases due to molecular freeze-out onto dust grains (freeze-out layer) by a factor of > 100 (CO) and 15 (CS). The H2CO emission decreases by a factor of only about 2, which is possibly due to H2CO formation on icy grains, followed by a nonthermal release into the gas phase. The inferred [CH3OH]/[H2CO] abundance ratio is 0.5−0.6, which is 1−2 orders of magnitude lower than for Class 0 hot corinos, and a factor ∼2.5 lower than the only other value inferred for a protoplanetary disk (in TW Hya, 1.3−1.7). Additionally, it is at the lower edge but still consistent with the values in comets. This may indicate that some chemical reprocessing occurs in disks before the formation of planets and comets

ALMA chemical survey of disk-outflow sources in Taurus (ALMA-DOT). IV. Thioformaldehyde (H<SUB>2</SUB>CS) in protoplanetary discs: spatial distributions and binding energies

International audienceContext. Planet formation starts around Sun-like protostars with ages ≤1 Myr, but the chemical compositions of the surrounding discs remains unknown. Aims: We aim to trace the radial and vertical spatial distribution of a key species of S-bearing chemistry, namely H2CS, in protoplanetary discs. We also aim to analyse the observed distributions in light of the H2CS binding energy in order to discuss the role of thermal desorption in enriching the gas disc component. Methods: In the context of the ALMA chemical survey of disk-outflow sources in the Taurus star forming region (ALMA-DOT), we observed five Class I or early Class II sources with the o-H2CS(71,6-61,5) line. ALMA-Band 6 was used, reaching spatial resolutions ≃40 au, that is, Solar System spatial scales. We also estimated the binding energy of H2CS using quantum mechanical calculations, for the first time, for an extended, periodic, crystalline ice. Results: We imaged H2CS emission in two rotating molecular rings in the HL Tau and IRAS 04302+2247 discs, the outer radii of which are ~140 au (HL Tau) and 115 au (IRAS 04302+2247). The edge-on geometry of IRAS 04302+2247 allows us to reveal that H2CS emission peaks at radii of 60-115 au, at z = ±50 au from the equatorial plane. Assuming LTE conditions, the column densities are ~1014 cm-2. We estimate upper limits of a few 1013 cm-2 for the H2CS column densities in DG Tau, DG Tau B, and Haro 6-13 discs. For HL Tau, we derive, for the first time, the [H2CS]/[H] abundance in a protoplanetary disc (≃10-14). The binding energy of H2CS computed for extended crystalline ice and amorphous ices is 4258 and 3000-4600 K, respectively, implying thermal evaporation where dust temperatures are ≥50-80 K. Conclusions: H2CS traces the so-called warm molecular layer, a region previously sampled using CS and H2CO. Thioformaldehyde peaks closer to the protostar than H2CO and CS, plausibly because of the relatively high excitation level of the observed 71,6-61,5 line (60 K). The H2CS binding energy implies that thermal desorption dominates in thin, au-sized, inner and/or upper disc layers, indicating that the observed H2CS emitting up to radii larger than 100 au is likely injected in the gas phase due to non-thermal processes. Reduced datacubes are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (ftp://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/cat/J/A+A/644/A120</A

ALMA chemical survey of disk-outflow sources in Taurus (ALMA-DOT)

The chemical composition of planets is determined by the distribution of the various molecular species in the protoplanetary disk at the time of their formation. To date, only a handful of disks have been imaged in multiple spectral lines with high spatial resolution. As part of a small campaign devoted to the chemical characterization of disk-outflow sources in Taurus, we report on new ALMA Band 6 (~1.3 mm) observations with ~0.15′′ (20 au) resolution toward the embedded young star DG Tau B. Images of the continuum emission reveals a dust disk with rings and, putatively, a leading spiral arm. The disk, as well as the prominent outflow cavities, are detected in CO, H2CO, CS, and CN; instead, they remain undetected in SO2, HDO, and CH3OH. From the absorption of the back-side outflow, we inferred that the disk emission is optically thick in the inner 50 au. This morphology explains why no line emission is detected from this inner region and poses some limitations toward the calculation of the dust mass and the characterization of the inner gaseous disk. The H2CO and CS emission from the inner 200 au is mostly from the disk, and their morphology is very similar. The CN emission significantly differs from the other two molecules as it is observed only beyond 150 au. This ring-like morphology is consistent with previous observations and the predictions of thermochemical disk models. Finally, we constrained the disk-integrated column density of all molecules. In particular, we found that the CH3OH/H2CO ratio must be smaller than ~2, making the methanol non-detection still consistent with the only such ratio available from the literature (1.27 in TW Hya)