OH Ice Research Articles

Detection of the elusive dangling OH ice features at ~2.7 μm in Chamaeleon I with JWST NIRCam

Detection of the elusive dangling OH ice features at ~2.7 μm in Chamaeleon I with JWST NIRCam

JWST detections of amorphous and crystalline HDO ice toward massive protostars

Tracing the origin and evolution of interstellar water is key to understanding many of the physical and chemical processes involved in star and planet formation. Deuterium fractionation offers a window into the physicochemical history of water due to its sensitivity to local conditions. The aim of this work is to utilize the increased sensitivity and resolution of the James Webb Space Telescope (JWST) to quantify the HDO/H$_ $O ratio in ices toward young stellar objects (YSOs) and to determine if the HDO/H$_ $O ratios measured in the gas phase toward massive YSOs (MYSOs) are representative of the ratios in their ice envelopes. Two protostars observed in the Investigating Protostellar Accretion (IPA) program using JWST NIRSpec were analyzed: HOPS 370, an intermediate-mass YSO (IMYSO), and IRAS 20126+4104, a MYSO. The HDO ice toward these sources was quantified via its 4.1 mu m band. The contributions from the CH$_ $OH combination modes to the observed optical depth in this spectral region were constrained via the CH$_ $OH 3.53 mu m band to ensure that the integrated optical depth of the HDO feature was not overestimated. H$_ $O ice was quantified via its 3 mu m band. New laboratory IR spectra of ice mixtures containing HDO, H$_ $O, CH$_ $OH, and CO were collected to aid in the fitting and chemical interpretation of the observed spectra. HDO ice is detected above the 3sigma level in both sources. It requires a minimum of two components, one amorphous and one crystalline, to obtain satisfactory fits. The H$_ $O ice band at 3 mu m similarly requires both amorphous and crystalline components. The observed peak positions of the crystalline HDO component are consistent with those of annealed laboratory ices, which could be evidence of heating and subsequent recooling of the ice envelope (i.e., thermal cycling). The CH$_ $OH 3.53 mu m band is fit best with two cold components, one consisting of pure CH$_ $OH and the other of CH$_ $OH in an H$_ $O-rich mixture. From these fits, ice HDO/H$_ $O abundance ratios of 4.6pm 1.8times 10$^ $ and 2.6pm 1.2times 10$^ $ are obtained for HOPS 370 and IRAS 20126+4104, respectively. The simultaneous detections of both crystalline HDO and crystalline H$_ $O corroborate the assignment of the observed feature at 4.1 mu m to HDO ice. The ice HDO/H$_ $O ratios are similar to the highest reported gas HDO/H$_ $O ratios measured toward MYSOs and the hot inner regions of isolated low-mass protostars, suggesting that at least some of the gas HDO/H$_ $O ratios measured toward massive hot cores are representative of the HDO/H$_ $O ratios in ices. The need for an H$_ $O-rich CH$_ $OH component in the CH$_ $OH ice analysis supports recent experimental and observational results that indicate that some CH$_ $OH ice may form prior to the CO freeze-out stage in H$_ $O-rich ice layers.

Simulation of CH3OH ice UV photolysis under laboratory conditions

Context. Methanol is the most complex molecule that is securely identified in interstellar ices. It is a key chemical species for understanding chemical complexity in astrophysical environments. Important aspects of the methanol ice photochemistry are still unclear, such as the branching ratios and photodissociation cross sections at different temperatures and irradiation fluxes. Aims. This work aims at a quantitative agreement between laboratory experiments and astrochemical modelling of the CH3OH ice UV photolysis. Ultimately, this work allows us to better understand which processes govern the methanol ice photochemistry present in laboratory experiments. Methods. We used the code ProDiMo to simulate the radiation fields, pressures, and pumping efficiencies characteristic of laboratory measurements. The simulations started with simple chemistry consisting only of methanol ice and helium to mimic the residual gas in the experimental chamber. A surface chemical network enlarged by photodissociation reactions was used to study the chemical reactions within the ice. Additionally, different surface chemistry parameters such as surface competition, tunnelling, thermal diffusion, and reactive desorption were adopted to check those that reproduce the experimental results. Results. The chemical models with the code ProDiMo that include surface chemistry parameters can reproduce the methanol ice destruction via UV photodissociation at temperatures of 20, 30, 50, and 70 K as observed in the experiments. We also note that the results are sensitive to different branching ratios after photolysis and to the mechanisms of reactive desorption. In the simulations of a molecular cloud at 20 K, we observed an increase in the methanol gas abundance of one order of magnitude, with a similar decrease in the solid-phase abundance. Conclusions. Comprehensive astrochemical models provide new insights into laboratory experiments as the quantitative understanding of the processes that govern the reactions within the ice. Ultimately, these insights can help us to better interpret astronomical observations.

Molecular synthesis in ices triggered by dissociative electron attachment to carbon monoxide

Chemical reactions in mixed molecular ices as relevant in the context of astrochemistry can be initiated by electron-molecule interactions. Dissociative electron attachment (DEA) as initiating step is identified from the enhancement of product yields upon irradiation at particular electron energies. Herein, we show that DEA to CO leads to the formation of HCN in mixed CO/hbox {NH}_{{3}} ice at electron energies around 11 eV and 16 eV. We propose that this reaction proceeds via insertion of the neutral C fragment into a N–H bond. In the case of CO/hbox {H}_{{2}}O and CO/hbox {CH}_{{3}}OH ices, a resonant enhancement of the yields of HCOOH and hbox {CH}_{{3}}OCHO, respectively, is observed around 10 eV. In both ices, both molecular constituents exhibit DEA processes in this energy range so that the energy-dependent product yield alone does not uniquely identify the relevant DEA channel. However, we demonstrate by comparing with earlier results on mixed ices where CO is replaced by hbox {C}_{{2}}hbox {H}_{{4}} that DEA to CO is again responsible for the enhanced product formation. In this case, hbox {O}^{cdot -} activates hbox {H}_{{2}}O or hbox {CH}_{{3}}OH which leads to the formation of larger products. We thus show that DEA to CO plays an important role in electron-induced syntheses in molecular ices.Graphical abstract

Solid CO2 in quiescent dense molecular clouds

Context. Carbon dioxide (CO2 ) is one of the most abundant species detected in icy grain mantles in star forming regions. Laboratory experiments have shown that CO2 molecules are efficiently formed in the solid state under interstellar conditions. Specifically, solid CO2 can be formed through energetic (e.g. UV photolysis, electron and ion bombardment) and non-energetic mechanisms (atom-addition reactions).Aims. Here we investigate the role of low-energy cosmic-ray bombardment in the formation of solid CO2 in quiescent dense molecular clouds.Methods. We performed laboratory experiments to study the formation of CO2 after ion irradiation with 200 keV H+ of astrophysical relevant ice mixtures. Laboratory spectra are used to fit the profile of the CO2 bending mode band observed at about 15.2 μ m (660 cm-1 ) by the Spitzer Space Telescope in the line of sight to background sources.Results. From a qualitative point of view, good fits to observations are obtained by considering either three or four laboratory components. From a quantitative point of view, a better result is obtained with four components, i.e. when a spectrum of CO2 formed after ion irradiation of CH3 OH ice is added to the fitting procedure.Conclusions. Our results support the hypothesis that energetic processing of icy grain mantles is an efficient formation mechanism of CO2 ice also in quiescent dark cloud regions, and indirectly suggest the presence of CH3 OH in icy grain mantles in interstellar cold regions.

Complex organic molecules in organic-poor massive young stellar objects

Massive young stellar objects (MYSOs) with hot cores are classic sources of complex organic molecules. The origins of these molecules in such sources, as well as the small- and large-scale differentiation between nitrogen- and oxygen-bearing complex species, are poorly understood. We aim to use complex molecule abundances toward a chemically less explored class of MYSOs with weak hot organic emission lines to constrain the impact of hot molecular cores and initial ice conditions on the chemical composition toward MYSOs. We use the IRAM 30m and the Submillimeter Array to search for complex organic molecules over 8-16 GHz in the 1~mm atmospheric window toward three MYSOs with known ice abundances, but without luminous molecular hot cores. Complex molecules are detected toward all three sources at comparable abundances with respect to CH$_3$OH to classical hot core sources. The relative importance of CH$_3$CHO, CH$_3$CCH, CH$_3$OCH$_3$, CH$_3$CN, and HNCO differ between the organic-poor MYSOs and hot cores, however. Furthermore, the N-bearing molecules are generally concentrated toward the source centers, while most O- and C-bearing molecules are present both in the center and in the colder envelope. Gas-phase HNCO/CH$_3$OH ratios are tentatively correlated with the ratios of NH$_3$ ice over CH$_3$OH ice in the same lines of sight, which is consistent with new gas-grain model predictions. Hot cores are not required to form complex organic molecules, and source temperature and initial ice composition both seem to affect complex organic distributions toward MYSOs. To quantify the relative impact of temperature and initial conditions requires, however, a larger spatially resolved survey of MYSOs with ice detections.

Interstellar ice analogs: band strengths of H2O, CO2, CH3OH, and NH3in the far-infrared region

We measure the band strengths in the far-infrared region of interstellar ice analogs of astrophysically relevant species, such as H$_2$O, CO$_2$, CH$_3$OH, and NH$_3$, deposited at low temperature (8-10 $\mathrm{K}$), followed by warm-up, to induce amorphous-crystalline phase transitions when relevant. The spectra of pure H$_2$O, NH$_3$, and CH$_3$OH ices have been measured in the near-, mid- and far-infrared spectroscopic regions using the Interstellar Astrochemistry Chamber (ISAC) ultra-high-vacuum setup. In addition, far-infrared spectra of NH$_3$ and CO$_2$ were measured using a different set-up equipped with a bolometer detector. Band strengths in the far-infrared region were estimated using the corresponding near- and mid-infrared values as a reference. We also performed theoretical calculations of the amorphous and crystalline structures of these molecules using solid state computational programs at density functional theory (DFT) level. Vibrational assignment and mode intensities for these ices were predicted. Infrared band strengths in the 25-500 ${\mu}$m range have been determined for the considered ice samples by direct comparison in the near- and mid-infrared regions. Our values were compared to those we calculated from the literature complex index of refraction. We found differences of a factor of two between the two sets of values. The calculated far-infrared band strengths provide a benchmark for interpreting the observational data from future space telescope missions, allowing the estimation of the ice column densities.

Methanol ice on the surface of minor bodies in the solar system

Aims. Spectral analyses of trans-Neptunan objects (TNOs) and of the linked Centaurs, which are supposed to be among the most primitive minor bodies in the solar system, reveal some chemical and physical properties of their surface. To determine the surface composition of these objects and their surface evolution is essential for gaining clues on the conditions under which the solar system has been formed. Methods. Chemical composition and physical properties of the surface of three objects have been constrained by computing the depth of the absorption features of the spectra in the near-infrared, running spectral models based on radiative transfer theory in the [0.4-2.3] μm range, and analyzing new laboratory measurements of the spectral behavior of thin samples of H 2 O-CH 3 OH mixtures. Results. Our investigations allow us to confirm the presence of CH 3 OH ice on the surface of the Centaur (5145) Pholus and the resonant (55638) TNO 2002 VE 95 . It may also possibly be found on the classical TNO (120348) 2004 TY 364 . Our laboratory experiments indicate that the behavior of the methanol and water ice absorption bands is dependent on the ambient temperature and the dilution level of the mixture. These results also suggest that methanol may be diluted in water ice on the surface of the Centaur Pholus. Conclusions. Formation and destruction processes of methanol suggest that a part (at least) of the surface of these objects is younger than the solar system age. If confirmed, this shows that primordial ices could still be detected on the surface of objects that are submitted to irradiation and rejuvenation processes.