arXiv subjects

Elettra L. Piacentino

Publications and source records attributed to Elettra L. Piacentino.

8 recordsLinked to original sources

arXiv2026

CO and N2 Produced from H2O, CO2, and NH3 Cometary Ice Analogs

Hypervolatile species such as carbon monoxide (CO) and molecular nitrogen (N2) have been detected in comets, and could be used to constrain comet formation temperature conditions if their presence is due to freeze-out and/or entrapment. Here we instead explore another plausible origin of cometary hypervolatiles: photodissociation of less volatile species. We characterize CO and N2 formation following ultraviolet (UV) irradiation and electron bombardment of carbon dioxide (CO2), ammonia (NH3), H2O:CO2, H2O:NH3, and H2O:CO2:NH3 cometary ice analogs. We find that CO and N2 form in all photoprocessed ices at temperatures between 10 K and 100 K, resulting in 0.4-0.9 % CO and 0.03-0.7 % N2 relative to water, and CO/CO2 and N2/NH3 mixing ratios of 2.5-62 % and 0.7-9 %, respectively, across the experiments. Because our initial ices are reasonably well-matched to interstellar ices and we use UV exposure similar to a dark cloud, we can compare the resulting ratios directly to cometary abundances. Such a comparison shows that while only a few of CO observations in comets are readily explained by photodissociation, almost all observed cometary N2 can be accounted for by photodissociation of NH3 embedded in water ice. The latter result is also consistent with observed similarly elevated isotopic ratios of N2 and NH3 in 67P. Taken together, our results suggest that N2/H2O ratios less than 1 % should be used cautiously when inferring a comet's formation location, while the more substantial CO abundances seen in many comets do likely imply entrapment at low ice temperatures.

astro-ph.EP↗

arXiv2026

Functionalization of Benzene Ices by Atomic Oxygen

Small aromatic molecules, including functionalized derivatives of benzene, are known to be present throughout the different stages of star and planet formation. In particular, oxygen-bearing monosubstituted aromatics, likely including phenol, have been identified in the coma of comet 67P. This suggests that, earlier in the star and planet formation evolution, icy grains may act as both reservoirs and sites of functionalization for these small aromatics. We investigate the ice-phase reactivity of singlet oxygen atoms (O($^1$D)) with benzene, using ozone as a precursor that is readily photodissociated by relatively low-energy. Our experiments show that O($^1$D) efficiently reacts with benzene, forming phenol, benzene oxide, and oxepine as the main products. Phenol formation is temperature-independent, consistent with a barrierless insertion mechanism. In contrast, the formation of benzene oxide/oxepine shows a slight temperature dependence, suggesting that additional reaction pathways involving either ground-state or excited-state oxygen atoms may contribute. In H$_2$O and \COO ice matrices we find that dilution does not suppress formation of phenol. We extrapolate an experimental upper limit for the benzene-to-phenol conversion fraction of 27-44$\%$ during the lifetime of an interstellar cloud, assuming O($^1$D) production rates based on CO$_2$ ice abundances and a cosmic-ray induced UV field. We compare these estimates with a new analysis of data from the comet 67P, where the C$_6$H$_6$O/C$_6$H$_6$ ratio is 20$\pm$6$\%$. This value lies within our estimated range, suggesting that O($^1$D)-mediated chemistry is a viable pathway for producing oxygenated aromatics in cold astrophysical ices, potentially enriching icy planetesimals with phenol and other biorelevant compounds.

astro-ph.EP↗

arXiv2025

The survival of aromatic molecules in protoplanetary disks

Aromaticity is a common chemical functionalities in bioactive molecules. In interstellar and circumstellar environments benzene and other small aromatics are considered the precursor for more complex prebiotic molecules and they have shown to potentially have rich ice-phase photochemistry. The availability of small organic molecules in prebiotic networks depends on their photostability in astrophysical environments preceding planet formation, particularly during the protoplanetary disk stage, as the disk composition is linked to the chemical make-up of planets and planetesimals. We study the ultraviolet (UV) photodestruction (120-160 nm) of five aromatic molecules in undiluted ices and, for selected cases, in astrophysically relevant ice matrices (H2O, CO, CO2). For each ice, we measure the destruction cross sections as a function of photon exposure. In undiluted ices, aromatic molecules exhibit substantially lower photodestruction cross sections (sigma < 10-19 cm2) than aliphatic hydrocarbons, including cyclohexane, (sigma = 2.8-4x10-18 cm2). Furthermore, neither substituent nature nor size affects the aromatic stability in pure ices, suggesting that the strong intermolecular interactions among aromatic molecules provide protection against VUV exposure, even with small to mid-sized ring substituents. In mixed ices, the photodestruction and reactivity of aromatic molecules (sigma = 2.5-6.1x10-18 cm2) increases by more than an order of magnitude, but are still lower than in the gas-phase. We attribute this to a weaker cage effect and matrix-specific interactions. We use the experimental photodestruction cross sections to estimate the lifetime of aromatic molecules in protoplanetary disks, denileating the disks regions in which aromatic photochemistry is expected to be the most active.

astro-ph.IM↗

arXiv2025

H2S ice sublimation dynamics: experimentally constrained binding energies, entrapment efficiencies, and snowlines

Hydrogen sulfide (H2S) is thought to be an important sulfur reservoir in interstellar ices. It serves as a key precursor to complex sulfur-bearing organics, and has been proposed to play a significant role in the origin of life. Although models and observations both suggest H2S to be present in ices in non-negligible amounts, its sublimation dynamics remain poorly constrained. In this work, we present a comprehensive experimental characterization of the sublimation behavior of H2S ice under astrophysically-relevant conditions. The sublimation behavior of H2S was monitored with a quadrupole mass spectrometer (QMS) during temperature-programmed desorption (TPD) experiments. These experiments are used to determine binding energies and entrapment efficiencies of H2S, which are then employed to estimate its snowline positions in a protoplanetary disk midplane. We derive mean binding energies of 3159\pm46 K for pure H2S ice and 3392\pm56 K for submonolayer H2S desorbing from a compact amorphous solid water (cASW) surface. These values correspond to sublimation temperatures of around 64 K and 69 K in the disk midplane, placing its sublimation fronts at radii just interior to the CO2 snowline. We also investigate the entrapment of H2S in water ice and find it to be highly efficient, with ~75-85% of H2S remaining trapped past its sublimation temperature for H2O:H2S mixing ratios of ~5-17:1. We discuss potential mechanisms behind this efficient entrapment. Our findings imply that, in protoplanetary disks, H2S will mostly be retained in the ice phase until water crystallizes, at radii near the water snowline, if it forms mixed into water ice. This has significant implications for the possibility of H2S being incorporated into icy planetesimals and its potential delivery to terrestrial planets, which we discuss in detail.

astro-ph.EP↗

arXiv2025

Thermal Desorption Kinetics, Binding Energies, and Entrapment of Methyl Mercaptan Ices

Organosulfur species are potential major carriers of sulfur in the interstellar medium, as well as interesting ingredients in prebiotic chemistry. The most fundamental question regarding these species is under which conditions they reside in the gas versus solid phase. Here, we characterize the thermal desorption kinetics, binding energies, and entrapment of the organosulfur methyl mercaptan (CH$_3$SH, or MeSH) in different ice environments, comparing them with those of methanol (CH$_3$OH, or MeOH) ices. The derived multi-layer (pure MeSH-MeSH) and sub-monolayer (layered MeSH-H$_2$O) binding energies are surprisingly similar, corresponding to snow line locations where the disk midplane temperature is ~105 K. In both H$_2$O-dominated and more realistic H$_2$O:CO$_2$-dominated ices, 100% of the MeSH is entrapped, almost exclusively desorbing at the molecular volcano desorption peak, indicating that MeSH is retained at the water snow line if initially mixed with water ice during formation. Additionally, the presence of MeSH in an ice mixture enhances the entrapment of CO$_2$ and MeOH (up to 100%) until the onset of volcano desorption; without MeSH, both desorb at their respective pure desorption temperatures and also co-desorb with water. Compared to MeOH, MeSH binds less well to water, explaining why MeSH escapes during water ice crystallization rather than co-desorbing with water. These results show the larger relative size of MeSH compared to MeOH significantly impacts its ability to bind to water and its entrapment efficiency. Therefore, molecular size plays an important role in the adsorption and retention of S-bearing organics and, in turn, other volatiles in ices.

astro-ph.EP↗

arXiv2024

Characterization of monosubstituted benzene ices

Aromatic structures are fundamental for key biological molecules such as RNA and metabolites and the abundances of aromatic molecules on young planets are therefore of high interest. Recent detections of benzonitrile and other aromatic compounds in interstellar clouds and comets have revealed a rich aromatic astrochemistry. In the cold phases of star and planet formation, most of these aromatic molecules are likely to reside in icy grain mantles, where they could be observed through IR spectroscopy. We present laboratory IR spectra of benzene and four monosubstituted benzene molecules -- toluene, phenol, benzonitrile and benzaldehyde -- to determine their IR ice absorbances in undiluted aromatic ices, and in mixtures with water and CO. We also characterize the aromatic ice desorption rates, and extract binding energies and respective pre-exponential factors using temperature programmed desorption experiments. We use these to predict at which protostellar and protoplanetary disk temperatures these molecules sublimate into the gas-phase. We find that benzene and mono-substituted benzene derivatives are low-volatility with binding energies in the 5220-8390 K (43-70 kJ/mol) range, which suggests that most of the chemistry of benzene and of functionalized aromatic molecules is to be expected to occur in the ice phase during star and planet formation.

physics.chem-ph↗

arXiv2024

JWST ice band profiles reveal mixed ice compositions in the HH 48 NE disk

Planet formation is strongly influenced by the composition and distribution of volatiles within protoplanetary disks. With JWST, it is now possible to obtain direct observational constraints on disk ices, as recently demonstrated by the detection of ice absorption features towards the edge-on HH 48 NE disk as part of the Ice Age Early Release Science program. Here, we introduce a new radiative transfer modeling framework designed to retrieve the composition and mixing status of disk ices using their band profiles, and apply it to interpret the H2O, CO2, and CO ice bands observed towards the HH 48 NE disk. We show that the ices are largely present as mixtures, with strong evidence for CO trapping in both H2O and CO2 ice. The HH 48 NE disk ice composition (pure vs. polar vs. apolar fractions) is markedly different from earlier protostellar stages, implying thermal and/or chemical reprocessing during the formation or evolution of the disk. We infer low ice-phase C/O ratios around 0.1 throughout the disk, and also demonstrate that the mixing and entrapment of disk ices can dramatically affect the radial dependence of the C/O ratio. It is therefore imperative that realistic disk ice compositions are considered when comparing planetary compositions with potential formation scenarios, which will fortunately be possible for an increasing number of disks with JWST.

astro-ph.EP↗

arXiv2022

Computational Estimation of the Binding Energies of POx and HPOx (x=2,3) Species

The distribution of molecules between the gas and solid phase during star and planet formation, determines the trajectory of gas and grain surface chemistry, as well as the delivery of elements to nascent planets. This distribution is primarily set by the binding energies of different molecules to water ice surfaces. We computationally estimated the binding energies of ten astrochemically relevant P-bearing species on water surface, we also validate our method for 20 species with known binding energies. We used DFT calculations (M06-2X/aug-cc-pVDZ) to calculate the energetics of molecules and water-molecule clusters (1-3 H$_2$O molecules) and from this determined the binding energy by comparing the complex and the separate molecule and cluster energies. We also explore whether these estimates can be improved by first calibrating our computational method using experimentally measured binding energies. Using the 20 reference molecules we find that the 2H$_2$O cluster size yields the best binding energy estimates and that the application of a calibration to the data may improve the results for some classes of molecules, including more refractory species. Based on these calculations we find that, small P-bearing molecules such as PH$_3$, PN, PO, HPO, PO$_2$ and POOH are relatively volatile and should desorb prior or concomitantly with water ice, while H$_2$PO, HPO$_2$, PO$_3$, PO$_2$OH can strongly bind to any hydroxylated surface, and will likely remain on the interstellar grains surface past the desorbtion of water ice. The depletion of P-carriers on grains constitute a pathway for the inclusion of Phosphorous molecules in planets and planetesimals.

astro-ph.SR↗