Experimental evidence for glass polymorphism in vitrified water droplets

The nature of amorphous ices has been debated for more than 35 years. In essence, the question is whether they are related to ice polymorphs or to liquids. The fact that amorphous ices are traditionally prepared from crystalline ice via pressure-induced amorphization has made a clear distinction tricky. In this work, we vitrify liquid droplets through cooling at ≥106 K ⋅ s−1 and pressurize the glassy deposit. We observe a first order–like densification upon pressurization and recover a high-density glass. The two glasses resemble low- and high-density amorphous ice in terms of both structure and thermal properties. Vitrified water shows all features that have been reported for amorphous ices made from crystalline ice. The only difference is that the hyperquenched and pressurized deposit shows slightly different crystallization kinetics to ice I upon heating at ambient pressure. This implies a thermodynamically continuous connection of amorphous ices with liquids, not crystals.

Theoretical Determination of Binding Energies of Small Molecules on Interstellar Ice Surfaces

The adsorption of a series of atoms and small molecules and radicals (H, C, N, O, NH, OH, H2O, CH3, and NH3) on hexagonal crystalline and amorphous ice clusters were obtained via classical molecular dynamics and electronic structure methods. The geometry and binding energies were calculated using a QMHigh:QMLow hybrid method on model clusters. Several combination of basis sets, density functionals and semi-empirical methods were compared and tested against previous works. More accurate binding energies were also refined via single point Coupled Cluster calculations. Most species, except carbon atom, physisorb on the surface, leading to rather small binding energies. The carbon atom forms a COH2 molecule and in some cases leads to the formation of a COH-H3O+ complex. Amorphous ices are characterized by slightly stronger binding energies than the crystalline phase. A major result of this work is to also access the dispersion of the binding energies since a variety of adsorption sites is explored. The interaction energies thus obtained may serve to feed or refine astrochemical models. The present methodology could be easily extended to other types of surfaces and larger adsorbates.

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

Context. 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.

Evidence for high-density liquid water between 0.1 and 0.3 GPa near 150 K

Thermal stability against crystallization upon isobaric heating at pressure 0.1 ≤ P ≤ 1.9 GPa is compared for five variants of high- (HDA) and very high-density amorphous ice (VHDA) with different preparation history. At 0.1–0.3 GPa expanded HDA (eHDA) and VHDA reach the same state before crystallization, which we infer to be the contested high-density liquid (HDL). Thus, 0.3 GPa sets the high-pressure limit for the possibility to observe HDL for timescales of minutes, hours, and longer. At P > 0.3 GPa the annealed amorphous ices no longer reach the same state before crystallization. Further examination of the results demonstrates that crystallization times are significantly affected both by the density of the amorphous matrix at the crystallization temperature Tx as well as by nanocrystalline domains remaining in unannealed HDA (uHDA) as a consequence of incomplete pressure-induced amorphization.