arXiv subjects

S. Ioppolo

Publications and source records attributed to S. Ioppolo.

At least 19 recordsLinked to original sources

arXiv2026

Infrared photoprocessing of porous amorphous solid water with a free electron laser

Water ice is the most abundant ice in the interstellar medium (ISM). Previous studies on porous amorphous solid water (pASW) have shown that the infrared radiation field in the ISM modeled with infrared free electron laser (FEL) irradiation can result in changes in the ice towards a more ordered structure, characterized by a change in the OH-stretching vibration band. This paper aims to study the restructuring in more detail by varying the irradiation intensity and irradiation time for irradiations on-resonance with the OH-stretching, bending and libration modes. In addition, desorption of H2O is monitored during the irradiations. The research presented in this paper considers 42 infrared FEL irradiations on pASW samples deposited at two different rates, using the infrared FELs of the HFML-FELIX laboratory. Restructuring is studied using reflection absorption infrared (RAIR) spectroscopy, with a mass spectrometer monitoring the desorption of H2O in an ultra-high vacuum system. Desorption and restructuring occur in parallel, with the strongest effects observed for irradiation on-resonance with the OH-stretching vibration. Both processes exhibit two distinct regimes: an initial strong restructuring and desorption, characterized by an exponential decrease in the intensity of the desorption peaks within the first 5 s of irradiation, followed by a second regime of less efficient, yet continued restructuring and constant desorption in an extended area, involving energy dissipation through the hydrogen-bonding network. The trends in restructuring and desorption, depending on the absorbed energy during irradiation, are significantly different, suggesting separate processes. The astrophysical relevance of in particular the second regime of constant desorption and restructuring is discussed.

astro-ph.GA↗

arXiv2025

UV irradiation of ethanol-containing interstellar ice analogs: Photostability in CH3CH2OH:CO mixtures

Ethanol (CH3CH2OH) has been detected in interstellar ices within regions associated with the early stages of star and planet formation. Its solid-phase pathways can lead to diverse conditions that can significantly influence its photostability and -chemistry. Laboratory studies have explored the effects of energetic processing on pure ethanol ices, there is a gap in understanding how ethanol behaves in astrophysically relevant mixed ices. This proof-of-principle study aims to quantify how the ice composition influences the photostability of ethanol mixed with CO, from both physical and chemical perspectives. It also seeks to highlight the importance of balancing constructive and destructive processes. Mixtures with ethanol to CO ratios ranging from 1:0 to 1:11 are exposed to UV irradiation from a microwave discharge H lamp under UHV conditions, at 16 K. The evolution of the solid phase is tracked using reflection-absorption infrared spectroscopy, and changes in the gas phase are monitored with a quadrupole mass spectrometer. Temperature-programmed desorption experiments aid in the identification of infrared spectral features. A radiative-transfer model has been developed to account for the influence of ice composition on the effective photon flux. The model reveals that, during later stages of irradiation, photoproducts play a significant role in the absorbing of incident photons, highlighting the complex cascade of processes initiated by single-photon absorption in ethanol-containing ices. By evaluating photodestruction cross sections as a function of the initial ice composition, we found that CO exerts a stabilizing effect on ethanol. For highly dilute ethanol:CO mixtures, representative of astronomical ices, the photodestruction cross section of ethanol is estimated to ~1.6E-17 cm2/photon after correcting for the effective absorbed UV fluence of the studied interstellar ice analogs.

astro-ph.GA↗

arXiv2025

CO desorption from interstellar icy grains induced by IR excitation of superhydrogenated PAHs

Infrared (IR) radiation dominates dense, interstellar clouds, yet its effect on icy grains remains largely unexplored. Its potential role in driving the photodesorption of volatile species from such grains has recently been demonstrated, providing a crucial link between the solid state reservoir of molecules and the gas phase. In this work, we investigate IR-induced photodesorption of CO for astrophysically relevant ice systems containing perhydropyrene (PHP). This fully superhydrogenated version of pyrene is used as an analogue for large carbonaceous molecules such as polycyclic aromatic hydrocarbons (PAHs) and related species, as well as hydrogenated carbonaceous grains. The abundance and range of strong IR absorption bands of these carbonaceous species make them interesting candidates for IR-induced effects. We present IR spectroscopic and mass spectrometric measurements probing the effects of IR radiation on two ice systems: a layered ice with CO on top of PHP, and a CO:PHP mixed ice. These ices were irradiated with IR radiation from the FELIX IR Free Electron Laser (FEL) FEL-2. In accordance with previous studies, we confirm that direct excitation of CO is not an efficient pathway to CO desorption, indicating that another energy dissipation mechanism exists. We demonstrate that vibrational excitation of the PHP CH stretching modes leads to efficient CO photodesorption. The derived photodesorption yields are an order of magnitude higher for the layered than the mixed system and comparable to those previously obtained for CO photodesorption from CO on amorphous solid water upon excitation of H$_2$O vibrational modes. Our results indicate that IR excitation of carbonaceous molecules and grains in dense clouds could potentially play an important role in the desorption of volatile species such as CO from icy grains.

astro-ph.GA↗

arXiv2024

Ice inventory towards the protostar Ced 110 IRS4 observed with the James Webb Space Telescope. Results from the ERS Ice Age program

This work focuses on the ice features toward the binary protostellar system Ced 110 IRS 4A and 4B, and observed with JWST as part of the Early Release Science Ice Age collaboration. We aim to explore the JWST observations of the binary protostellar system Ced~110~IRS4A and IRS4B to unveil and quantify the ice inventories toward these sources. We compare the ice abundances with those found for the same molecular cloud. The analysis is performed by fitting or comparing laboratory infrared spectra of ices to the observations. Spectral fits are carried out with the ENIIGMA fitting tool that searches for the best fit. For Ced~110~IRS4B, we detected the major ice species H$_2$O, CO, CO$_2$ and NH$_3$. All species are found in a mixture except for CO and CO$_2$, which have both mixed and pure ice components. In the case of Ced~110~IRS4A, we detected the same major species as in Ced~110~IRS4B, as well as the following minor species CH$_4$, SO$_2$, CH$_3$OH, OCN$^-$, NH$_4^+$ and HCOOH. Tentative detection of N$_2$O ice (7.75~$\mu$m), forsterite dust (11.2~$\mu$m) and CH$_3^+$ gas emission (7.18~$\mu$m) in the primary source are also presented. Compared with the two lines of sight toward background stars in the Chameleon I molecular cloud, the protostar has similar ice abundances, except in the case of the ions that are higher in IRS4A. The clearest differences are the absence of the 7.2 and 7.4~$\mu$m absorption features due to HCOO$^-$ and icy complex organic molecules in IRS4A and evidence of thermal processing in both IRS4A and IRS4B as probed by the CO$_2$ ice features. We conclude that the binary protostellar system Ced~110~IRS4A and IRS4B has a large inventory of icy species. The similar ice abundances in comparison to the starless regions in the same molecular cloud suggest that the chemical conditions of the protostar were set at earlier stages in the molecular cloud.

astro-ph.SR↗

arXiv2024

AQUILA: A Laboratory Facility for the Irradiation of Astrochemical Ice Analogues by keV Ions

The detection of various molecular species, including complex organic molecules relevant to biochemical and geochemical processes, in astronomical settings such as the interstellar medium or the outer Solar System has led to the increased need for a better understanding of the chemistry occurring in these cold regions of space. In this context, the chemistry of ices prepared and processed at cryogenic temperatures has proven to be of particular interest due to the fact that many interstellar molecules are believed to originate within the icy mantles adsorbed on nano- and micro-scale dust particles. The chemistry leading to the formation of such molecules may be initiated by ionising radiation in the form of galactic cosmic rays or stellar winds, and thus there has been an increased interest in commissioning experimental set-ups capable of simulating and better characterising this solid-phase radiation astrochemistry. In this article, we describe a new facility called AQUILA (Atomki-Queen's University Ice Laboratory for Astrochemistry) which has been purposefully designed to study the chemical evolution of ices analogous to those that may be found in the dense interstellar medium or the outer Solar System as a result of their exposure to keV ion beams. The results of some ion irradiation studies of CH3OH ice at 20 K are discussed to exemplify the experimental capabilities of the AQUILA as well as to highlight its complementary nature to another laboratory astrochemistry set-up at our institute.

astro-ph.IM↗

arXiv2024

A JWST/MIRI analysis of the ice distribution and PAH emission in the protoplanetary disk HH 48 NE

Ice-coated dust grains provide the main reservoir of volatiles that play an important role in planet formation processes and may become incorporated into planetary atmospheres. However, due to observational challenges, the ice abundance distribution in protoplanetary disks is not well constrained. We present JWST/MIRI observations of the edge-on disk HH 48 NE carried out as part of the IRS program Ice Age. We detect CO$_2$, NH$_3$, H$_2$O and tentatively CH$_4$ and NH$_4^+$. Radiative transfer models suggest that ice absorption features are produced predominantly in the 50-100 au region of the disk. The CO$_2$ feature at 15 micron probes a region closer to the midplane (z/r = 0.1-0.15) than the corresponding feature at 4.3 micron (z/r = 0.2-0.6), but all observations trace regions significantly above the midplane reservoirs where we expect the bulk of the ice mass to be located. Ices must reach a high scale height (z/r ~ 0.6; corresponding to modeled dust extinction Av ~ 0.1), in order to be consistent with the observed vertical distribution of the peak ice optical depths. The weakness of the CO$_2$ feature at 15 micron relative to the 4.3 micron feature and the red emission wing of the 4.3 micron CO$_2$ feature are both consistent with ices being located at high elevation in the disk. The retrieved NH$_3$ abundance and the upper limit on the CH$_3$OH abundance relative to H$_2$O are significantly lower than those in the interstellar medium (ISM), but consistent with cometary observations. Full wavelength coverage is required to properly study the abundance distribution of ices in disks. To explain the presence of ices at high disk altitudes, we propose two possible scenarios: a disk wind that entrains sufficient amounts of dust, thus blocking part of the stellar UV radiation, or vertical mixing that cycles enough ices into the upper disk layers to balance ice photodesorption.

astro-ph.EP↗

arXiv2024

A deep search for large complex organic species toward IRAS16293-2422 B at 3 mm with ALMA

Complex organic molecules (COMs) have been detected ubiquitously in protostellar systems. However, at shorter wavelengths (~0.8mm) it is more difficult to detect larger molecules than at longer wavelengths (~3mm) because of the increase of millimeter dust opacity, line confusion, and unfavorable partition function. We aim to search for large molecules (>8 atoms) in the ALMA Band 3 spectrum of IRAS 16293-2422 B. We search for more than 70 molecules and identify as many lines as possible in the spectrum. The spectral settings were set to specifically target three-carbon species such as propanol and glycerol. We identify lines of 31 molecules including many oxygen-bearing COMs such as CH3OH and c-C2H4O and a few nitrogen- and sulfur-bearing ones such as HOCH2CN and CH3SH. The largest detected molecules are gGg-(CH2OH)2 and CH3COCH3. We do not detect glycerol or propanol but provide upper limits for them which are in line with previous laboratory and observational studies. The line density in Band 3 is only ~2.5 times lower in frequency space than in Band 7. From the detected lines in Band 3 at a $\gtrsim 6σ$ level, ~25-30% of them could not be identified indicating the need for more laboratory data of rotational spectra. We find similar column densities and column density ratios of COMs (within a factor ~2) between Band 3 and Band 7. The effect of dust optical depth for IRAS 16293-2422 B at an off-source location on column densities and column density ratios is minimal. Moreover, for warm protostars, long wavelength spectra are not only crowded, but also take longer integration times to reach the same sensitivity limit. The 3mm search has not yet resulted in detection of larger and more complex molecules in warm sources. A full deep ALMA Band 2-3 (i.e., 3-4 mm) survey is needed to assess whether low frequency data have the potential to reveal more complex molecules in warm sources.

astro-ph.GA↗

arXiv2023

A JWST inventory of protoplanetary disk ices: The edge-on protoplanetary disk HH 48 NE, seen with the Ice Age ERS program

Ices are the main carriers of volatiles in protoplanetary disks and are crucial to our understanding of the chemistry that ultimately sets the organic composition of planets. The ERS program Ice Age on the JWST follows the ice evolution through all stages of star and planet formation. JWST/NIRSpec observations of the edge-on Class II protoplanetary disk HH~48~NE reveal spatially resolved absorption features of the major ice components H$_2$O, CO$_2$, CO, and multiple weaker signatures from less abundant ices NH$_3$, OCN$^-$, and OCS. Isotopologue $^{13}$CO$_2$ ice has been detected for the first time in a protoplanetary disk. Since multiple complex light paths contribute to the observed flux, the ice absorption features are filled in by ice-free scattered light. The $^{12}$CO$_2$/$^{13}$CO$_2$ ratio of 14 implies that the $^{12}$CO$_2$ feature is saturated, without the flux approaching 0, indicative of a very high CO$_2$ column density on the line of sight, and a corresponding abundance with respect to hydrogen that is higher than ISM values by a factor of at least a few. Observations of rare isotopologues are crucial, as we show that the $^{13}$CO$_2$ observation allows us to determine the column density of CO$_2$ to be at an order of magnitude higher than the lower limit directly inferred from the observed optical depth. Radial variations in ice abundance, e.g., snowlines, are significantly modified since all observed photons have passed through the full radial extent of the disk. CO ice is observed at perplexing heights in the disk, extending to the top of the CO-emitting gas layer. We argue that the most likely interpretation is that we observe some CO ice at high temperatures, trapped in less volatile ices like H$_2$O and CO$_2$. Future radiative transfer models will be required to constrain the implications on our current understanding of disk physics and chemistry.

astro-ph.EP↗

arXiv2023

CoCCoA: Complex Chemistry in hot Cores with ALMA. Selected oxygen-bearing species

Complex organic molecules (COMs) have been observed to be abundant in the gas phase toward protostars. Deep line surveys have been carried out only for a limited number of well-known high-mass star forming regions using the Atacama Large Millimeter/submillimeter Array (ALMA), which has unprecedented resolution and sensitivity. Statistical studies on oxygen-bearing COMs (O-COMs) in high-mass protostars using ALMA are still lacking. With the recent CoCCoA survey, we are able to determine the column density ratios of six O-COMs with respect to methanol (CH$_3$OH) in a sample of 14 high-mass protostellar sources to investigate their origin through ice and/or gas-phase chemistry. The selected species are: acetaldehyde (CH$_3$CHO), ethanol (C$_2$H$_5$OH), dimethyl ether (DME, CH$_3$OCH$_3$), methyl formate (MF, CH$_3$OCHO), glycolaldehyde (GA, CH$_2$OHCHO), and ethylene glycol (EG, (CH$_2$OH)$_2$). DME and MF have the highest and most constant ratios within one order of magnitude, while the other four species have lower ratios and exhibit larger scatter by 1-2 orders of magnitude. We compare the O-COM ratios of high-mass CoCCoA sources with those of 5 low-mass protostars available from the literature, along with the results from experiments and simulations. We find that the O-COM ratios with respect to methanol are on the same level in both the high- and low-mass samples, which suggests that these species are mainly formed in similar environments during star formation, probably in ice mantles on dust grains during early pre-stellar stages. Current simulations and experiments can reproduce most observational trends with a few exceptions, and hypotheses exist to explain the differences between observations and simulations/experiments, such as the involvement of gas-phase chemistry and different emitting areas of molecules.

astro-ph.GA↗

arXiv2023

The edge-on protoplanetary disk HH 48 NE II. Modeling ices and silicates

The abundance and distribution of ice in protoplanetary disks (PPD) is critical to understand the linkage between the composition of circumstellar matter and the composition of exoplanets. Edge-on PPDs are a useful tool to constrain such ice composition and its location in the disk, as ice spectral signatures can be observed in absorption against the continuum emission arising from the warmer central disk regions. The aim of this work is to model ice absorption features in PPDs and determine how well the abundance of the main ice species across the disk can be determined within the uncertainty of the physical parameter space. The edge-on PPD around HH 48 NE, a target of the JWST ERS program IceAge, is used as a reference system. We use RADMC-3D to raytrace the mid-infrared continuum. Using a constant parameterized ice abundance, ice opacities are added to the dust opacity in regions wherever the disk is cold enough for the main carbon, oxygen and nitrogen carriers to freeze out. The global abundance of the main ice carriers in HH 48 NE can be determined within a factor of 3, when taking the uncertainty of the physical parameters into account. Ice features in PPDs can be saturated at an optical depth <1, due to local saturation. Spatially observed ice optical depths cannot be directly related to column densities due to radiative transfer effects. Vertical snowlines will not be a clear transition due to the radially increasing height of the snowsurface, but their location may be constrained from observations using radiative transfer modeling. Radial snowlines are not really accesible. Not only the ice abundance, but also inclination, settling, grain size distribution and disk mass have strong impact on the observed ice absorption features in disks. Relative changes in ice abundance can be inferred from observations only if the source structure is well constrained

astro-ph.EP↗

arXiv2023

The edge-on protoplanetary disk HH 48 NE I. Modeling the geometry and stellar parameters

Context. Observations of edge-on disks are an important tool for constraining general protoplanetary disk properties that cannot be determined in any other way. However, most radiative transfer models cannot simultaneously reproduce the spectral energy distributions (SEDs) and resolved scattered light and submillimeter observations of these systems, due to the differences in geometry and dust properties at different wavelengths. Aims. We simultaneously constrain the geometry of the edge-on protoplanetary disk HH 48 NE and the characteristics of the host star. HH 48 NE is part of the JWST early release science program Ice Age. This work serves as a stepping stone towards a better understanding of the disk physical structure and icy chemistry in this particular source. This kind of modeling lays the groundwork for studying other edge-on sources to be observed with the JWST. Methods. We fit a parameterized dust model to HH 48 NE by coupling the radiative transfer code RADMC-3D and an MCMC framework. The dust structure was fitted independently to a compiled SED, a scattered light image at 0.8 $μ$m and an ALMA dust continuum observation at 890 $μ$m. Results. We find that 90% of the dust mass in HH 48 NE is settled to the disk midplane, less than in average disks, and that the atmospheric layers of the disk contain exclusively large grains (0.3-10 $μ$m). The exclusion of small grains in the upper atmosphere likely has important consequences for the chemistry due to the deep penetration of high-energy photons. The addition of a relatively large cavity (ca. 50 au in radius) is necessary to explain the strong mid-infrared emission, and to fit the scattered light and continuum observations simultaneously.

astro-ph.EP↗

arXiv2023

Resonant infrared irradiation of CO and CH3OH interstellar ices

Solid-phase photo-processes involving icy dust grains greatly affect the chemical evolution of the interstellar medium by leading to the formation of complex organic molecules and by inducing photodesorption. So far, the focus of laboratory studies has been mainly on the impact of energetic ultraviolet (UV) photons on ices, but direct vibrational excitation by infrared (IR) photons is expected to influence the morphology and content of interstellar ices as well. However, little is still known about the mechanisms through which this excess vibrational energy is dissipated, and its implications on the structure and ice photochemistry. In this work, we present a systematic investigation of the behavior of interstellar relevant CO and CH3OH ice analogues upon resonant excitation of vibrational modes using tunable infrared radiation, leading to both the quantification of infrared-induced photodesorption and insights in the impact of vibrational energy dissipation on ice morphology. We utilize an ultrahigh vacuum setup at cryogenic temperatures to grow pure CO and CH3OH ices, as well as mixtures of the two. We expose the ices to intense, near-monochromatic mid-infrared free-electron-laser radiation to selectively excite the species. The dissipation of vibrational energy is observed to be highly dependent on the excited mode and the chemical environment of the ice. All amorphous ices undergo some degree of restructuring towards a more organized configuration upon on-resonance irradiation. Moreover, IR-induced photodesorption is observed to occur for both pure CO and CH3OH ices, with interstellar photodesorption efficiencies of the order of 10 molecules cm-2 s-1 (i.e., comparable to or higher than UV-induced counterparts). Indirect photodesorption of CO upon vibrational excitation of CH3OH in ice mixtures is also observed to occur, particularly in environments rich in methanol.

astro-ph.GA↗

arXiv2023

An Ice Age JWST inventory of dense molecular cloud ices

Icy grain mantles are the main reservoir of the volatile elements that link chemical processes in dark, interstellar clouds with the formation of planets and composition of their atmospheres. The initial ice composition is set in the cold, dense parts of molecular clouds, prior to the onset of star formation. With the exquisite sensitivity of JWST, this critical stage of ice evolution is now accessible for detailed study. Here we show the first results of the Early Release Science program "Ice Age" that reveal the rich composition of these dense cloud ices. Weak ices, including, $^{13}$CO$_2$, OCN$^-$, $^{13}$CO, OCS, and COMs functional groups are now detected along two pre-stellar lines of sight. The $^{12}$CO$_2$ ice profile indicates modest growth of the icy grains. Column densities of the major and minor ice species indicate that ices contribute between 2 and 19% of the bulk budgets of the key C, O, N, and S elements. Our results suggest that the formation of simple and complex molecules could begin early in a water-ice rich environment.

astro-ph.GA↗

arXiv2022

Sulfur Ion Implantations Into Condensed CO2: Implications for Europa

The ubiquity of sulfur ions within the Jovian magnetosphere has led to suggestions that the implantation of these ions into the surface of Europa may lead to the formation of SO2. However, previous studies on the implantation of sulfur ions into H2O ice (the dominant species on the Europan surface) have failed to detect SO2 formation. Other studies concerned with similar implantations into CO2 ice, which is also known to exist on Europa, have offered seemingly conflicting results. In this letter, we describe the results of a study on the implantation of 290 keV S+ ions into condensed CO2 at 20 and 70 K. Our results demonstrate that SO2 is observed after implantation at 20 K, but not at the Europa-relevant temperature of 70 K. We conclude that this process is likely not a reasonable mechanism for SO2 formation on Europa, and that other mechanisms should be explored instead.

astro-ph.EP↗

arXiv2022

TeraHertz Desorption Emission Spectroscopy (THz DES) of space relevant ices

We present an experimental instrument that performs laboratory-based gas-phase Terahertz Desorption Emission Spectroscopy (THz-DES) experiments in support of astrochemistry. The measurement system combines a terahertz heterodyne radiometer that uses room temperature semiconductor mixer diode technology previously developed for the purposes of Earth observation, with a high-vacuum desorption gas cell and high-speed digital sampling circuitry to enable high spectral and temporal resolution spectroscopy of molecular species with thermal discrimination. During use, molecules are condensed onto a liquid nitrogen cooled metal finger to emulate ice structures that may be present in space. Following deposition, thermal desorption is controlled and initiated by means of a heater and monitored via a temperature sensor. The 'rest frequency' spectral signatures of molecules released into the vacuum cell environment are detected by the heterodyne radiometer in real-time and characterised with high spectral resolution. To demonstrate the viability of the instrument, we have studied Nitrous Oxide (N2O). This molecule strongly emits within the terahertz (sub-millimetre wavelength) range and provide a suitable test gas and we compare the results obtained with more traditional techniques such as quadrupole mass spectrometry. The results obtained allow us to fully characterize the measurement method and we discuss its potential use as a laboratory tool in support of astrochemical observations of molecular species in the interstellar medium and the Solar System.

astro-ph.IM↗

arXiv2022

On the origin of molecular oxygen on the surface of Ganymede

Since its first identification on the surface of Ganymede in 1995, molecular oxygen (O2) ice has been at the center of a scientific debate as the surface temperature of the Jovian moon is on average well above the freezing point of O2. Laboratory evidence suggested that solid O2 may either exist in a cold (<50 K) subsurface layer of the icy surface of Ganymede, or it is in an atmospheric haze of the moon. Alternatively, O2 is constantly replenished at the surface through ion irradiation of water-containing ices. A conclusive answer on the existence of solid O2 on the surface of Ganymede is hampered by the lack of detailed, extensive observational datasets. We present new ground-based, high-resolution spectroscopic observations of Ganymede's surface obtained at the Telescopio Nazionale Galileo. These are combined with dedicated laboratory measurements of ultraviolet-visible (UV-vis) photoabsorption spectra of O2 ice, both pure and mixed with other species of potential interest for the Galilean satellites. Our study confirms that the two bands identified in the visible spectra of Ganymede's surface are due to the (1,0) and (0,0) transition bands of O2 ice. Oxygen-rich ice mixtures including water (H2O) and carbon dioxide (CO2) can reproduce observational reflectance data of the Ganymede's surface better than pure O2 ice in the temperature range 20-35 K. Solid H2O and CO2 also provide an environment where O2 ice can be trapped at higher temperatures than its pure ice desorption under vacuum space conditions. Our experiments at different temperatures show also that the (1,0)/(0,0) ratio in case of the CO2:O2=1:2 ice mixture at 35 K has the closest value to observations, while at 30 K the (1,0)/(0,0) ratio seems to be mixture independent with the exception of the N2:O2=1:2 ice mixture. The present work will support the ESA/JUICE mission to the Jovian system.

astro-ph.EP↗

arXiv2022

IRFEL Selective Irradiation of Amorphous Solid Water: from Dangling to Bulk Modes

Amorphous solid water (ASW) is one of the most widely studied solid phase systems. A better understanding of the nature of inter- and intramolecular forces in ASW is, however, still required to correctly interpret the catalytic role of ASW in the formation and preservation of molecular species in environments such as the icy surfaces of Solar System objects, on interstellar icy dust grains and potentially even in the upper layers of the Earth's atmosphere. In this work, we have systematically exposed porous ASW (pASW) to mid-infrared radiation generated by a free-electron laser at the HFML-FELIX facility in the Netherlands to study the effect of vibrational energy injection into the surface and bulk modes of pASW. During multiple sequential irradiations on the same ice spot, we observed selective effects both at the surface and in the bulk of the ice. Although the density of states in pASW should allow for a fast vibrational relaxation through the H-bonded network, part of the injected energy is converted into structural ice changes as illustrated by the observation of spectral modifications when performing Fourier transform infrared spectroscopy in reflection-absorption mode. Future studies will include the quantification of such effects by systematically investigating ice thickness, ice morphology, and ice composition.

physics.chem-ph↗

arXiv2020

Vacuum ultraviolet photoabsorption spectroscopy of space-related ices: Formation and destruction of solid carbonic acid upon 1~keV electron irradiation

Carbonic acid (H2CO3) is a weak acid relevant to astrobiology which, to date, remains undetected in space. Experimental work has shown that the beta-polymorph of H2CO3 forms under space relevant conditions through energetic (UV photon, electron, and cosmic ray) processing of CO2- and H2O-rich ices. We present a systematic set of VUV photoabsorption spectra of pure and mixed CO2 and H2O ices exposed to 1 keV electrons at 20 and 80 K to simulate different interstellar and Solar System environments. Ices were then annealed to obtain a layer of pure H2CO3 which was further exposed to 1 keV electrons at 20 and 80 K to monitor its destruction pathway. Fourier-transform infrared (FT-IR) spectroscopy was used as a secondary probe providing complementary information on the physicochemical changes within an ice. Our laboratory work shows that the formation of solid H2CO3, CO, and O3 upon the energetic processing of CO2:H2O ice mixtures is temperature-dependent in the range between 20 and 80 K. The amorphous to crystalline phase transition of H2CO3 ice is investigated for the first time in the VUV spectral range by annealing the ice at 200 and 225 K. We have detected two photoabsorption bands at 139 and 200 nm, and we assigned them to beta-H2CO3 and gamma-H2CO3, respectively. We present VUV spectra of the electron irradiation of annealed H2CO3 ice at different temperatures leading to its decomposition into CO2, H2O, and CO ice. Laboratory results are compared to Cassini UltraViolet Imaging Spectrograph observations of the 70-90 K ice surface of Saturn's satellites Enceladus, Dione, and Rhea.

astro-ph.IM↗