Search

Carbonyl sulfide (OCS) is widely observed in the gas phase towards star-forming regions and was the first of the only two sulfur-bearing species detected in interstellar ices so far. However, the chemical network governing its formation is still not fully understood. While the sulfurization of CO and the oxidation of CS are often invoked to form OCS, other mechanisms could have a significant contribution. In particular, the multistep reaction involving CO and SH is a good candidate to forming OCS in dense cloud environments. We aim to constrain the viability of the CO + SH route to forming solid OCS in the interstellar medium, in a similar manner as CO + OH is known to produce CO2 ice. This is achieved by conducting a systematic laboratory investigation of the targeted reactions on interstellar ice analogues under dense cloud conditions. An ultrahigh vacuum chamber is utilized to simultaneously deposit CO, H2S, and atomic H at 10 K. SH radicals produced in situ via hydrogen abstraction from H2S react with CO to form OCS. OCS is efficiently formed through surface reactions involving CO, H2S, and H atoms. The suggested underlying mechanism behind OCS formation is CO + SH -> HSCO followed by HSCO + H -> OCS + H2. The OCS yield reduces slowly, but remains significant with increasing CO:H2S mixing ratios (CO:H2S = 1:1, 5:1, 10:1, and 20:1). Our experiments provide unambiguous evidence that OCS can be formed from CO + SH in the presence of H atoms. This route remains efficient for large H2S dilutions (5% w.r.t CO), suggesting that it is a viable mechanism in interstellar ices. Given that SH radicals can be created in clouds throughout a wide evolutionary timescale, this mechanism could have a non-negligible contribution to forming interstellar OCS ice., Comment: 7 pages, 4 figures, 1 table, accepted for publication in A&A on August 6th, 2024

The chemical network governing interstellar sulfur has been the topic of unrelenting discussion for the past decades due to the conspicuous discrepancy between its expected and observed abundances in different interstellar environments. More recently, the astronomical detections of CH3CH2SH and CH2CS highlighted the importance of interstellar formation routes for sulfur-bearing organic molecules with two carbon atoms. In this work, we perform a laboratory investigation of the solid-state chemistry resulting from the interaction between C2H2 molecules and SH radicals -- both thought to be present in interstellar icy mantles -- at 10 K. Reflection absorption infrared spectroscopy and quadrupole mass spectrometry combined with temperature-programmed desorption experiments are employed as analytical techniques. We confirm that SH radicals can kick-start a sulfur reaction network under interstellar cloud conditions and identify at least six sulfurated products: CH3CH2SH, CH2CHSH, HSCH2CH2SH, H2S2, and tentatively CH3CHS and CH2CS. Complementarily, we utilize computational calculations to pinpoint the reaction routes that play a role in the chemical network behind our experimental results. The main sulfur-bearing organic molecule formed under our experimental conditions is CH3CH2SH and its formation yield increases with the ratios of H to other reactants. It serves as a sink to the sulfur budget within the network, being formed at the expense of the other unsaturated products. The astrophysical implications of the chemical network proposed here are discussed., Comment: 9 figures, 2 pages, Accepted for publication in ACS Earth and Space Chemistry on July 5th 2024

Ice mantles play a crucial role in shaping the astrochemical inventory of molecules during star and planet formation. Small-scale molecular processes have a profound impact on large-scale astronomical evolution. The areas of solid-state laboratory astrophysics and computational chemistry study these processes. We review the laboratory effort on ice spectroscopy; methodological advances and challenges; and laboratory and computational studies of ice physics and ice chemistry. The latter we put in context with the ice evolution from clouds to disks. Three takeaway messages from this review are - Laboratory and computational studies allow interpretation of astronomical ice spectra in terms of identification, ice morphology and, local environmental conditions as well as the formation of the involved chemical compounds. - A detailed understanding of the underlying processes is needed to build reliable astrochemical models to make predictions on the abundances in space. - The relative importance of the different ice processes studied in the laboratory and computationally changes along the process of star and planet formation., Comment: 48 pages, 9 figures

This work aims to utilize the increased sensitivity and resolution of the JWST to quantify the HDO/H$_{2}$O ratio in ices toward young stellar objects (YSOs) and to determine if the HDO/H$_{2}$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 detected above the 3$\sigma$ level and quantified via its 4.1 $\mu$m band. The contributions from the CH$_{3}$OH combination modes to the observed optical depth in this spectral region were constrained via the CH$_{3}$OH 3.53 $\mu$m band to ensure that the integrated optical depth of the HDO feature was not overestimated. H$_{2}$O ice was quantified via its 3 $\mu$m band. From these fits, ice HDO/H$_{2}$O abundance ratios of 4.6$\pm$1.8$\times$10$^{-3}$ and 2.6$\pm$1.2$\times$10$^{-3}$ are obtained for HOPS 370 and IRAS 20126+4104, respectively. The simultaneous detections of both crystalline HDO and crystalline H$_{2}$O corroborate the assignment of the observed feature at 4.1 $\mu$m to HDO ice. The ice HDO/H$_{2}$O ratios are similar to the highest reported gas HDO/H$_{2}$O ratios measured toward MYSOs as well as the hot inner regions of isolated low-mass protostars, suggesting that at least some of the gas HDO/H$_{2}$O ratios measured toward massive hot cores are representative of the HDO/H$_{2}$O ratios in ices. The need for an H$_{2}$O-rich CH$_{3}$OH component in the CH$_{3}$OH ice analysis supports recent experimental and observational results that indicate that some CH$_{3}$OH ice may form prior to the CO freeze-out stage in H$_{2}$O-rich ice layers., Comment: Accepted for publication in A&A. 23 pages, 17 figures, 10 tables

Accretion and ejection sets the outcome of the star and planet formation process. The mid-infrared wavelength range offers key tracers of those processes that were difficult to detect and spatially resolve in protostars until now. We aim to characterize the interplay between accretion and ejection in the low-mass Class I protobinary system TMC1, comprising two young stellar objects: TMC1-W and TMC1-E with 85 au separation. With the {\it James Webb} Space Telescope (JWST) - Mid-Infrared Instrument (MIRI) observations in 5 - 28 $\mu$m range, we measure intensities of emission lines of H$_2$, atoms and ions, e.g., [Fe II] and [Ne II], and HI recombination lines. We detect H$_2$ outflow coming from TMC1-E, with no significant H$_2$ emission from TMC1-W. The H$_2$ emission from TMC1-E outflow appears narrow and extends to wider opening angles with decreasing E$_{up}$ from S(8) to S(1) rotational transitions, indicating a disk wind origin. The outflow from TMC1-E protostar shows spatially extended emission lines of [Ne II], [Ne III], [Ar II], and [Ar III], with their line ratios consistent with UV radiation as a source of ionization. With ALMA, we detect accretion streamer infalling from $>$ 1000 au scales onto the TMC1-E component. TMC1-W protostar powers a collimated jet, detected with [Fe II] and [Ni II] consistent with energetic flow. A much weaker ionized jet is observed from TMC1-E. TMC1-W is associated with strong emission from hydrogen recombination lines, tracing the accretion onto the young star. Observations of a binary Class I protostellar system show that the two processes are clearly intertwined, with accretion from the envelope onto the disk influencing a wide-angle wind ejected on disk scales, while accretion from the protostellar disk onto the protostar is associated with the source launching a collimated high-velocity jet within the innermost regions of the disk., Comment: 18 pages, 13 figures, accepted for publication in Astronomy and Astrophysics

The structure and composition of simple ices can be modified during stellar evolution by protostellar heating. Key to understanding the involved processes are thermal and chemical tracers that can diagnose the history and environment of the ice. The 15.2 $\mu$m bending mode of $^{12}$CO$_2$ has proven to be a valuable tracer of ice heating events but suffers from grain shape and size effects. A viable alternative tracer is the weaker $^{13}$CO$_2$ isotopologue band at 4.39 $\mu$m which has now become accessible at high S/N with the $\textit{James Webb}$ Space Telescope (JWST). We present JWST NIRSpec observations of $^{13}$CO$_2$ ice in five deeply embedded Class 0 sources spanning a wide range in luminosities (0.2 - 10$^4$ L$_{\odot}$ ) taken as part of the Investigating Protostellar Accretion Across the Mass Spectrum (IPA) program. The band profiles vary significantly, with the most luminous sources showing a distinct narrow peak at 4.38 $\mu$m. We first apply a phenomenological approach and show that a minimum of 3-4 Gaussian profiles are needed to fit the $^{13}$CO$_2$ absorption feature. We then combine these findings with laboratory data and show that a 15.2 $\mu$m $^{12}$CO$_2$ band inspired five-component decomposition can be applied for the isotopologue band where each component is representative of CO$_2$ ice in a specific molecular environment. The final solution consists of cold mixtures of CO$_2$ with CH$_3$OH, H$_2$O and CO as well as segregated heated pure CO$_2$ ice. Our results are in agreement with previous studies of the $^{12}$CO$_2$ ice band, further confirming that $^{13}$CO$_{2}$ is a useful alternative tracer of protostellar heating events. We also propose an alternative solution consisting only of heated CO$_2$:CH$_3$OH and CO$_2$:H$_2$O ices and warm pure CO$_2$ ice for decomposing the ice profiles of the two most luminous sources in our sample.

We carried out a sensitive survey of C$_2$ and C$_3$ using the EDIBLES data set. We also expanded our searches to C$_4$, C$_5$, and $^{13}$C$^{12}$C isotopologue in the most molecule-rich sightlines. We fit synthetic spectra generated following a physical excitation model to the C$_2$ (2-0) Phillips band to obtain the C$_2$ column density ($N$) as well as the kinetic temperature ($T_\textrm{kin}$) and number density ($n$) of the host cloud. The C$_3$ molecule was measured through its $\tilde{A} - \tilde{X}$ (000-000) electronic origin band system. We simulated the excitation of this band with a double-temperature Boltzmann distribution. We present the largest combined survey of C$_2$ and C$_3$ to date in which the individual transitions can be resolved. In total we detected C$_2$ in 51 velocity components along 40 sightlines, and C$_3$ in 31 velocity components along 27 sightlines. The two molecules are detected in the same velocity components. We find a very good correlation between $N$(C$_2$) and $N$(C$_3$) with Pearson $r = 0.93$ and an average $N$(C$_2$)/$N$(C$_3$) ratio of 15.5$\pm$1.4. A comparison with the behaviour of the C$_2$ DIBs shows that there are no clear differences among sightlines with and without detection of C$_2$ and C$_3$. This is in direct contrast to the better-studied non-C$_2$ DIBs who have reduced strengths in molecule-rich environments. We also identify for the first time the $Q$(2), $Q$(3), and $Q$(4) transitions of the $^{13}$C$^{12}$C (2-0) Phillips band in a stacked average spectrum, and estimate the isotopic ratio of carbon $^{12}$C/$^{13}$C as 79$\pm$8. Our search for the C$_4$ and C$_5$ optical bands was unsuccessful., Comment: 31 pages, 23 figures. To appear in A&A

Interstellar lines observed toward stellar targets change slowly over long timescales, mainly due to the proper motion of the background target relative to the intervening clouds. On longer timescales, the cloud's slowly changing physical and chemical conditions can also cause variation. We searched for systematic variations in the absorption profiles of the diffuse interstellar bands (DIBs) and interstellar atomic and molecular lines by comparing the high-quality data set from the ESO diffuse interstellar bands extensive exploration survey (EDIBLES) to older archival observations, bridging typical timescales of 10 years with a maximum timescale of 22 years. We found good archival observations for 64 EDIBLES targets. Our analysis focused on 31 DIBs, 7 atomic, and 5 molecular lines. We considered various systematic effects and applied a robust Bayesian test to establish which absorption features could display significant variations. While systematic effects greatly complicate our search, we find evidence for variations in the profiles of the $\lambda\lambda$4727 and 5780 DIBs in a few sightlines. Toward HD~167264, we find a new \ion{Ca}{i} cloud component that appears and becomes stronger after 2008. The same sightline furthermore displays marginal but systematic changes in the column densities of the atomic lines originating from the leading cloud component in the sightline. Similar variations are seen toward HD~147933. Our high-quality spectroscopic observations and archival data show that it is possible to probe interstellar time variations on time scales of typically a decade. Even though systematic uncertainties, as well as the generally somewhat lower quality of older data, complicate matters, we can conclude that time variations can be made visible, both in atomic lines and DIB profiles for a few targets, but that generally, these features are stable along many lines of sight., Comment: 180 pages, 138 figures, accepted for publication in A&A journal

Hydrogen sulfide (H$_2$S) is thought to be efficiently formed on grain surfaces through the successive hydrogenation of S atoms. Its non-detection so far in astronomical observations of icy dust mantles thus indicates that effective destruction pathways must play a significant role in its interstellar abundance. While chemical desorption has been shown to remove H$_2$S very efficiently from the ice, in line with H$_2$S gas-phase detections, possible solid-state chemistry triggered by the related HS radical have been largely disregarded so far -- despite it being an essential intermediate in the H$_2$S + H reaction scheme. We aim to thoroughly investigate the fate of H$_2$S upon H-atom impact under molecular cloud conditions, providing a comprehensive analysis combined with detailed quantification of both the chemical desorption and ice chemistry that ensues. Experiments are performed in an ultrahigh vacuum chamber at temperatures between 10--16 K. The changes in the solid phase during H-atom bombardment are monitored in situ by means of reflection absorption infrared spectroscopy (RAIRS), and desorbed species are measured with a quadrupole mass spectrometer (QMS). We confirm the formation of H$_2$S$_2$ via reactions involving H$_2$S + H, and quantify its formation cross section under the employed experimental conditions. Additionally, we directly assess the chemical desorption of H$_2$S by measuring the gas-phase desorption signals with the QMS, providing unambiguous desorption cross sections. Chemical desorption of H$_2$S$_2$ was not observed. The relative decrease of H$_2$S ices by chemical desorption changes from ~85% to ~74% between temperatures of 10 and 16 K, while the decrease as the result of H$_2$S$_2$ formation is enhanced from ~5% to ~26%, suggesting an increasingly relevant sulfur chemistry induced by HS radicals at warmer environments. The astronomical implications are further discussed., Comment: 11 pages, 9 Figures, 3 Tables. Accepted for publication in Astronomy and Astrophysics

This work aims at characterizing the mid-IR spectra of formamide in its pure form as well as in mixtures of the most abundant interstellar ices via laboratory simulation of such ices, as well as demonstrating how these laboratory spectra can be used to search for formamide in ice observations. Mid-IR spectra (4000 - 500 cm$^{-1}$, 2.5 - 20 $\mu$m) of formamide, both in its pure form as well as in binary and tertiary mixtures with H$_2$O, CO$_2$, CO, NH$_3$, CH$_3$OH, H$_2$O:CO$_2$, H$_2$O:NH$_3$, CO:NH$_3$, and CO:CH$_3$OH, are collected at temperatures ranging from 15 - 212 K. Apparent band strengths and positions of eight IR bands of pure amorphous and crystalline formamide at various temperatures are provided. Three bands are identified as potential formamide tracers in observational ice spectra: the overlapping C=O stretch and NH$_2$ scissor bands at 1700.3 and 1630.4 cm$^{-1}$ (5.881 and 6.133 $\mu$m), the CH bend at 1388.1 cm$^{-1}$ (7.204 $\mu$m), and the CN stretch at 1328.1 cm$^{-1}$ (7.529 $\mu$m). The relative apparent band strengths, positions, and FWHM of these features in mixtures at various temperatures are also determined. Finally, the laboratory spectra are compared to observational spectra of low- and high-mass young stellar objects as well as pre-stellar cores observed with the Infrared Space Observatory, the Spitzer Space Telescope, and the JWST. A comparison between the formamide CH bend in laboratory data and the 7.24 $\mu$m band in the observations tentatively indicates that, if formamide ice is contributing significantly to the observed absorption, it is more likely in a polar matrix. Upper limits ranging from 0.35-5.1\% with respect to H$_{2}$O are calculated. These upper limits are in agreement with gas-phase formamide abundances and take into account the effect of a H$_{2}$O matrix on formamide's band strengths., Comment: Accepted for publication in A&A. 25 pages, 11 figures, 9 tables

C$_3$, a pure carbon chain molecule that has been identified in different astronomical environments, is considered a good probe of kinetic temperatures through observation of transitions involving its low-lying bending mode ($\nu_2$) in its ground electronic state. The present laboratory work aims to investigate this bending mode with multiple quanta of excitation by combining recordings of high resolution optical and infrared spectra of C$_3$ produced in discharge experiments. The optical spectra of rovibronic (A $^1\Pi_u -$ X $^1\Sigma_g^+$) transitions have been recorded by laser induced fluorescence spectroscopy using a single longitude mode optical parametric oscillator as narrow bandwidth laser source at the University of Science and Technology of China. 36 bands originating from X(0$v_2$0), $v_2 = 0-5$, are assigned. The mid-infrared spectrum of the rovibrational $\nu_3$ band has been recorded by Fourier-transform infrared spectroscopy using a globar source on the AILES beamline of the SOLEIL synchrotron facility. The spectrum reveals hot bands involving up to 5 quanta of excitation in $\nu_2$. From combining analyses of all the presently recorded spectra and literature data, accurate rotational parameters and absolute energy levels of C$_3$, in particular for states involving the bending mode, are determined. A single PGOPHER file containing all available data involving the X and A states (literature and present study) is used to fit all the data. The spectroscopic information derived from this work enables new interstellar searches for C$_3$, not only in the infrared and optical regions investigated here but also notably in the $\nu_2$ band region (around 63 cm$^{-1}$) where vibrational satellites can now be accurately predicted. This makes C$_3$ a universal diagnostic tool to study very different astronomical environments, from dark and dense to translucent clouds., Comment: 15 pages, 9 figures, 4 tables

The increasing sensitivity and resolution of ground-based telescopes have enabled the detection of gas-phase complex organic molecules (COMs) across a variety of environments. Many of the detected species are expected to form on the icy surface of interstellar grains and transfer later into the gas phase. Therefore, icy material is regarded as a primordial source of COMs in the ISM. Upcoming JWST observations of interstellar ices in star-forming regions will reveal IR features of frozen molecules with unprecedented resolution and sensitivity. To identify COM features in the JWST data, lab IR spectra of ices for conditions that simulate interstellar environments are needed. This work presents FTIR spectra (500-4000 cm$^{-1}$/20-2.5$\mu$m, with a resolution of 1 cm$^{-1}$) of methyl cyanide (CH$_3$CN, aka acetonitrile) mixed with H$_2$O, CO, CO$_2$, CH$_4$, and NH$_3$, at temperatures from 15-150 K. The refractive index of pure amorphous CH$_3$CN ice at 15K and the band strength, peak position, and FWHM of selected IR bands are also measured. These bands are: the CH$_3$ sym stretching at 2940.9 cm$^{-1}$, the CN stretching at 2252.2 cm$^{-1}$, a combination of modes at 1448.3 cm$^{-1}$ , the CH$_3$ antisym def. at 1410 cm$^{-1}$ , the CH$_3$ sym def. at 1374.5 cm$^{-1}$, and the CH$_3$ rock at 1041.6 cm$^{-1}$. The lab spectra of CH$_3$CN are compared to observations of ices toward W33A and three low-mass YSOs. Since an unambiguous identification of CH$_3$CN is not possible, upper limits for the CH$_3$CN column density are determined as $\leq 2.4\times 10^{17}$ molecules cm$^{-2}$ for W33A and $5.2 \times 10^{16}$, $1.9\times 10^{17}$, and $3.8\times 10^{16}$ molecules cm$^{-2}$ for EC92, IRAS 03235, and L1455 IRS3, respectively. W.r.t solid H$_2$O, these values correspond to relative abundances of 1.9, 3.1, 1.3, and 4.1\%, for W33A, EC92, IRAS 03235, and L1455 IRS3, respectively., Comment: 26 pages, 11 figures, accepted for publication in A&A

The successive addition of H atoms to CO in the solid phase has been hitherto regarded as the primary route to form methanol in dark molecular clouds. However, recent Monte Carlo simulations of interstellar ices alternatively suggested the radical-molecule H-atom abstraction reaction CH3O + H2CO -> CH3OH + HCO, in addition to CH3O + H -> CH3OH, as a very promising and possibly dominating (70 - 90 %) final step to form CH3OH in those environments. Here, we compare the contributions of these two steps leading to methanol by experimentally investigating hydrogenation reactions on H2CO and D2CO ices, which ensures comparable starting points between the two scenarios. The experiments are performed under ultrahigh vacuum conditions and astronomically relevant temperatures, with H:H2CO (or D2CO) flux ratios of 10:1 and 30:1. The radical-molecule route in the partially deuterated scenario, CHD2O + D2CO -> CHD2OD + DCO, is significantly hampered by the isotope effect in the D-abstraction process, and can thus be used as an artifice to probe the efficiency of this step. We observe a significantly smaller yield of D2CO + H products in comparison to H2CO + H, implying that the CH3O-induced abstraction route must play an important role in the formation of methanol in interstellar ices. Reflection-Absorption InfraRed Spectroscopy (RAIRS) and Temperature Programmed Desorption-Quadrupole Mass Spectrometry (TPD-QMS) analyses are used to quantify the species in the ice. Both analytical techniques indicate constant contributions of ~80 % for the abstraction route in the 10 - 16 K interval, which agrees well with the Monte Carlo conclusions. Additional H2CO + D experiments confirm these conclusions., Comment: 10 pages, 1 table, 6 figures. Accepted in the Astrophysical Journal Letters

Several diffuse interstellar bands (DIBs) have profiles with resolved sub-peaks that resemble rotational bands of large molecules. Analysis of these profiles can constrain the sizes and geometries of the DIB carriers, especially if the profiles exhibit clear variations along lines of sight probing different physical conditions. Using the extensive data set from the EDIBLES survey we searched for systematic variations in the peak-to-peak separation of these sub-peaks for the $\lambda\lambda$5797, 6379, and 6614 DIBs in lines of sight with a single dominant interstellar cloud. We used the spectra of twelve single-cloud sight lines to measure the peak-to-peak separation in the band profile substructures for these DIBs. We adopted the rotational contour formalism to infer the rotational constant for each DIB carrier and the rotational excitation temperature in the sight lines. We compared these to rotational constants for linear and spherical molecules to estimate the DIB carrier sizes. All three DIBs have peak separations that vary systematically between lines of sight, indicating correlated changes in the rotational excitation temperatures. We derived $B_{6614}$=$(22.2\pm8.9)\times 10^{-3}$ cm$^{-1}$, consistent with previous estimates. Assuming a similar rotational temperature for the $\lambda$6614 DIB carrier and assuming a linear carrier, we found B$_{5797}^{\rm linear}=(5.1\pm2.0)\times10^{-3}~{\rm cm}^{-1}$ and B$_{6379}^{\rm linear} =(2.3\pm0.9)\times10^{-3}~{\rm cm}^{-1}$. If the carriers of those DIBs however are spherical species, their rotational constants are half that value, $B_{5797}^{\rm spherical} = (2.6\pm1.0)\times10^{-3}~{\rm cm}^{-1}$ and $B_{6379}^{\rm spherical} = (1.1\pm0.4)\times10^{-3}~{\rm cm}^{-1}$. We estimate molecule sizes that range from 7--9 carbon atoms ($\lambda$6614 carrier, linear) to 77--114 carbon atoms ($\lambda$6379, spherical)., Comment: 21 pages, 56 figures. Accepted for publication in Astronomy & Astrophysics

This work aims to constrain the abundances of interstellar amides, by searching for this group of prebiotic molecules in the intermediate-mass protostar Serpens SMM1-a. ALMA observations are conducted toward Serpens SMM1. A spectrum is extracted toward the SMM1-a position and analyzed with the CASSIS line analysis software for the presence of characteristic rotational lines of a number of amides and other molecules. NH$_{2}$CHO, NH$_{2}$CHO $\nu_{12}$=1, NH$_{2}^{13}$CHO, CH$_{3}$C(O)NH$_{2}$ $\nu$=0,1, CH$_{2}$DOH, CH$_{3}$CHO, and CH$_{3}$C(O)CH$_{3}$ are securely detected, while trans-NHDCHO, NH$_{2}$CDO, CH$_{3}$NHCHO $\nu$=0,1, CH$_{3}$COOH, and HOCH$_{2}$CHO are tentatively identified. The results of this work are compared with detections presented in the literature. A uniform CH$_{3}$C(O)NH$_{2}$/NH$_{2}$CHO ratio is found for a group of interstellar sources with vast physical differences. A similar ratio is seen for CH$_{3}$NHCHO, based on a smaller data sample. The D/H ratio of NH$_{2}$CHO is about 1--3\% and is close to values found in the low-mass source IRAS~16293--2422B. The formation of CH$_{3}$C(O)NH$_{2}$ and NH$_{2}$CHO is likely linked. Formation of these molecules on grain surfaces during the dark cloud stage is a likely scenario. The high D/H ratio of NH$_{2}$CHO is also seen as an indication that these molecules are formed on icy dust grains. As a direct consequence, amides are expected to be present in the most pristine material from which planetary systems form, thus providing a reservoir of prebiotic material., Comment: Accepted for publication in ACS Earth and Space Chemistry; 59 pages, 10 figures

The evolution of star-forming regions and their thermal balance are strongly influenced by their chemical composition, that, in turn, is determined by the physico-chemical processes that govern the transition between the gas phase and the solid state, specifically icy dust grains (e.g., particles adsorption and desorption). Gas-grain and grain-gas transitions as well as formation and sublimation of interstellar ices are thus essential elements of understanding astrophysical observations of cold environments (e.g., pre-stellar cores) where unexpected amounts of a large variety of chemical species have been observed in the gas phase. Adsorbed atoms and molecules also undergo chemical reactions which are not efficient in the gas phase. Therefore, the parameterization of the physical properties of atoms and molecules interacting with dust grain particles is clearly a key aspect to interpret astronomical observations and to build realistic and predictive astrochemical models. In this consensus evaluation, we focus on parameters controlling the thermal desorption of ices and how these determine pathways towards molecular complexity and define the location of snowlines, which ultimately influence the planet formation process. We review different crucial aspects of desorption parameters both from a theoretical and experimental point of view. We critically assess the desorption parameters commonly used in the astrochemical community for astrophysical relevant species and provide tables with recommended values. In addition, we show that a non-trivial determination of the pre-exponential factor nu using the Transition State Theory can affect the binding energy value. Finally, we conclude this work by discussing the limitations of theoretical and experimental approaches currently used to determine the desorption properties with suggestions for future improvements., Comment: 115 pages, 17 figures

Methoxymethanol (CH3OCH2OH, MM) has been identified through gas-phase signatures in both high- and low-mass star-forming regions. This molecule is expected to form upon hydrogen addition and abstraction reactions in CO-rich ice through radical recombination of CO hydrogenation products. The goal of this work is to investigate experimentally and theoretically the most likely solid-state MM reaction channel -- the recombination of CH2OH and CH3O radicals -- for dark interstellar cloud conditions and to compare the formation efficiency with that of other species that were shown to form along the CO-hydrogenation line. Hydrogen atoms and CO or H2CO molecules are co-deposited on top of the predeposited H2O ice to mimic the conditions associated with the beginning of 'rapid' CO freeze-out. Quadrupole mass spectrometry is used to analyze the gas-phase COM composition following a temperature programmed desorption. Monte Carlo simulations are used for an astrochemical model comparing the MM formation efficiency with that of other COMs. Unambiguous detection of newly formed MM has been possible both in CO+H and H2CO+H experiments. The resulting abundance of MM with respect to CH3OH is about 0.05, which is about 6 times less than the value observed toward NGC 6334I and about 3 times less than the value reported for IRAS 16293B. The results of astrochemical simulations predict a similar value for the MM abundance with respect to CH3OH factors ranging between 0.06 to 0.03. We find that MM is formed by co-deposition of CO and H2CO with H atoms through the recombination of CH2OH and CH3O radicals. In both the experimental and modeling studies, the efficiency of this channel alone is not sufficient to explain the observed abundance of MM. These results indicate an incomplete knowledge of the reaction network or the presence of alternative solid-state or gas-phase formation mechanisms., Comment: 8 pages, 8 figures

Laboratory results of the optical properties of vapor-deposited water ice, specifically the refractive index and extinction coefficient, are available mainly for a selective set of wavelengths and a limited number of deposition temperatures. Experimental limitations are the main reason for the lack of broadband data, which is unfortunate as these quantities are needed to interpret and predict astronomical and planetary observations. The goal of this work is to address these lacking data, using an experimental broadband method that is capable of rapidly providing reliable water ice data across the entire UV-visible range. This approach combines the simultaneous use of a monochromatic HeNe laser and a broadband Xe-arc lamp to record interference fringes of water ice during deposition at astronomically relevant ice temperatures. The ice thickness is typically more than 20 $\mu$m. Analyzing the period and intensity patterns combining both the monochromatic and broadband interference patterns allows the determination of the wavelength-dependent refractive index and extinction coefficient. We present accurate refractive index and extinction coefficient graphs for wavelengths between 250 and 750 nm and ices deposited between 30 and 160 K. From our data, we find a possible structural change in the ice in the 110-130 K region that has not been reported before. We also discuss that the data presented in this paper can be used to interpret astronomical observations of icy surfaces., Comment: 16 pages, 13 figures

Simple and complex organic molecules (COMs) are observed along different phases of star and planet formation and have been successfully identified in prestellar environments such as dark and translucent clouds. Yet the picture of organic molecule formation at those earliest stages of star formation is not complete and an important reason is the lack of specific laboratory experiments that simulate carbon atom addition reactions on icy surfaces of interstellar grains. Here we present experiments in which CO molecules as well as C- and H-atoms are co-deposited with H$_2$O molecules on a 10 K surface mimicking the ongoing formation of an "H$_2$O-rich" ice mantle. To simulate the effect of impacting C-atoms and resulting surface reactions with ice components, a specialized C-atom beam source is used, implemented on SURFRESIDE$^3$, an UHV cryogenic setup. Formation of ketene (CH$_2$CO) in the solid state is observed "in situ" by means of reflection absorption IR spectroscopy. C$^1$$^8$O and D isotope labelled experiments are performed to further validate the formation of ketene. Data analysis supports that CH$_2$CO is formed through C-atom addition to a CO-molecule, followed by successive hydrogenation transferring the formed :CCO into ketene. Efficient formation of ketene is in line with the absence of an activation barrier in C+CO reaction reported in the literature. We also discuss and provide experimental evidence for the formation of acetaldehyde (CH$_3$CHO) and possible formation of ethanol (CH$_3$CH$_2$OH), two COM derivatives of CH$_2$CO hydrogenation. The underlying reaction network is presented and the astrochemical implications of the derived pathways are discussed., Comment: Accepted by ApJ

We report new computational and experimental evidence of an efficient and astrochemically relevant formation route to formaldehyde (H$_2$CO). This simplest carbonylic compound is central to the formation of complex organics in cold interstellar clouds, and is generally regarded to be formed by the hydrogenation of solid-state carbon monoxide. We demonstrate H$_2$CO formation via the reaction of carbon atoms with amorphous solid water. Crucial to our proposed mechanism is a concerted proton transfer catalyzed by the water hydrogen bonding network. Consequently, the reactions $^3$C + H$_2$O -> $^3$HCOH and $^1$HCOH -> $^1$H$_2$CO can take place with low or without barriers, contrary to the high-barrier traditional internal hydrogen migration. These low barriers or absence thereof explain the very small kinetic isotope effect in our experiments when comparing the formation of H$_2$CO to D$_2$CO. Our results reconcile the disagreement found in the literature on the reaction route: C + H$_2$O -> H$_2$CO., Comment: Accepted for publication in JPCL

Methane is typically thought to be formed in the solid state on the surface of cold interstellar icy grain mantles via the successive atomic hydrogenation of a carbon atom. In the current work we investigate the potential role of molecular hydrogen in the CH$_4$ reaction network. We make use of an ultra-high vacuum cryogenic setup combining an atomic carbon atom beam and both atomic and/or molecular beams of hydrogen and deuterium on a H$_2$O ice. These experiments lead to the formation of methane isotopologues detected in situ through reflection absorption infrared spectroscopy. Most notably, CH$_4$ is formed in an experiment combining C atoms with H$_2$ on amorphous solid water, albeit slower than in experiments with H atoms present. Furthermore, CH$_2$D$_2$ is detected in an experiment of C atoms with H$_2$ and D$_2$ on H$_2$O ice. CD$_4$, however, is only formed when D atoms are present in the experiment. These findings have been rationalized by means of computational chemical insights. This leads to the following conclusions: a) the reaction C + H$_2$ -> CH$_2$ can take place, although not barrierless in the presence of water, b) the reaction CH + H$_2$ -> CH$_3$ is barrierless, but has not yet been included in astrochemical models, c) the reactions CH$_2$ + H$_2$ -> CH$_3$ + H and CH$_3$ + H$_2$ -> CH$_4$ + H can take place only via a tunneling mechanism and d) molecular hydrogen possibly plays a more important role in the solid-state formation of methane than assumed so far., Comment: Submitted to ApJ

Context. Infrared spectroscopy of star and planet forming regions is at the dawn of a new age with the upcoming James Webb Space Telescope. In support of these observations, laboratory spectra are required to identify complex organic molecules in the ices that cover the dust grains in these regions. Aims. This study aims to provide reference spectra to firmly detect icy methyl formate in the different stages of star and planet forming regions. Methyl formate is mixed in astronomically relevant matrices, and the peak positions, FWHMs, and relative band intensities are characterized for different temperatures to provide an analytical tool for astronomers. Methods. Methyl formate is deposited at 15 K under high-vacuum conditions. Specifically, methyl formate is deposited pure and mixed with CO, H$_2$CO, CH$_3$OH, H$_2$O, and CO:H$_2$CO:CH$_3$OH combined. Throughout the experiment infrared spectra are acquired with a FTIR spectrometer in the range from 4000-500 cm$^{-1}$ (2.5-20 $\mu$m) at a spectral resolution of 0.5 cm$^{-1}$. Results. We present the characterization of five solid-state methyl formate vibrational modes in pure and astronomically relevant ice matrices. The five selected vibrational modes, namely the C=O stretch, C$-$O stretch, CH$_3$ rocking, O$-$CH$_3$ stretching, and OCO deformation, are best suited for a JWST identification of methyl formate. For each of these vibrational modes, and each of the mixtures the TvS heatmaps, peak position versus FWHM, and relative band intensities are given. Additionally, the acquired reference spectra of methyl formate are compared with Spitzer observations of HH 46. A tentative detection of methyl formate provides an upper limit to the column density of $1.7\times10^{17}$ cm$^{-2}$, corresponding to an upper limit relative to water of $\leq 2.2\%$ and $\leq 40\%$ with respect to methanol., Comment: Accepted for publication in A&A

The vibrationally resolved spectra of the pyrene cation and doubly-dehydrogenated pyrene cation (C$_{16}$H$_{10}$$^{.+}$; Py$^+$ and C$_{16}$H$_{8}$$^{.+}$; ddPy$^+$) are presented. Infrared predissociation spectroscopy is employed to measure the vibrational spectrum of both species using a cryogenically cooled 22-pole ion trap. The spectrum of Py$^+$ allows a detailed comparison with harmonic and anharmonic density functional theory (DFT) calculated normal mode frequencies. The spectrum of ddPy$^+$ is dominated by absorption features from two isomers (4,5-ddPy$^+$ and 1,2-ddPy$^+$) with, at most, minor contributions from other isomers. These findings can be extended to explore the release of hydrogen from interstellar PAH species. Our results suggest that this process favours the loss of adjacent hydrogen atoms., Comment: 13 pages, 7 figures, supplementary information included

Exocomets are small bodies releasing gas and dust which orbit stars other than the Sun. Their existence was first inferred from the detection of variable absorption features in stellar spectra in the late 1980s using spectroscopy. More recently, they have been detected through photometric transits from space, and through far-IR/mm gas emission within debris disks. As (exo)comets are considered to contain the most pristine material accessible in stellar systems, they hold the potential to give us information about early stage formation and evolution conditions of extra Solar Systems. In the Solar System, comets carry the physical and chemical memory of the protoplanetary disk environment where they formed, providing relevant information on processes in the primordial solar nebula. The aim of this paper is to compare essential compositional properties between Solar System comets and exocomets. The paper aims to highlight commonalities and to discuss differences which may aid the communication between the involved research communities and perhaps also avoid misconceptions. Exocomets likely vary in their composition depending on their formation environment like Solar System comets do, and since exocomets are not resolved spatially, they pose a challenge when comparing them to high fidelity observations of Solar System comets. Observations of gas around main sequence stars, spectroscopic observations of "polluted" white dwarf atmospheres and spectroscopic observations of transiting exocomets suggest that exocomets may show compositional similarities with Solar System comets. The recent interstellar visitor 2I/Borisov showed gas, dust and nuclear properties similar to that of Solar System comets. This raises the tantalising prospect that observations of interstellar comets may help bridge the fields of exocomet and Solar System comets., Comment: 25 pages, 3 figures. To be published in PASP. This paper is the product of a workshop at the Lorentz Centre in Leiden, the Netherlands

A long standing problem in astrochemistry is the inability of many current models to account for missing sulfur content. Many relatively simple species that may be good candidates to sequester sulfur have not been measured experimentally at the high spectral resolution necessary to enable radioastronomical identification. On the basis of new laboratory data, we report searches for the rotational lines in the microwave, millimeter, and sub-millimeter regions of the sulfur-containing hydrocarbon HCCSH. This simple species would appear to be a promising candidate for detection in space owing to the large dipole moment along its $b$-inertial axis, and because the bimolecular reaction between two highly abundant astronomical fragments (CCH and SH radicals) may be rapid. An inspection of multiple line surveys from the centimeter to the far-infrared toward a range of sources from dark clouds to high-mass star-forming regions, however, resulted in non-detections. An analogous search for the lowest-energy isomer, H$_2$CCS, is presented for comparison, and also resulted in non-detections. Typical upper limits on the abundance of both species relative to hydrogen are $10^{-9}$-$10^{-10}$. We thus conclude that neither isomer is a major reservoir of interstellar sulfur in the range of environments studied. Both species may still be viable candidates for detection in other environments or at higher frequencies, providing laboratory frequencies are available., Comment: Accepted in the Astrophysical Journal

We are now on a clear trajectory for improvements in exoplanet observations that will revolutionize our ability to characterize their atmospheric structure, composition, and circulation, from gas giants to rocky planets. However, exoplanet atmospheric models capable of interpreting the upcoming observations are often limited by insufficiencies in the laboratory and theoretical data that serve as critical inputs to atmospheric physical and chemical tools. Here we provide an up-to-date and condensed description of areas where laboratory and/or ab initio investigations could fill critical gaps in our ability to model exoplanet atmospheric opacities, clouds, and chemistry, building off a larger 2016 white paper, and endorsed by the NAS Exoplanet Science Strategy report. Now is the ideal time for progress in these areas, but this progress requires better access to, understanding of, and training in the production of spectroscopic data as well as a better insight into chemical reaction kinetics both thermal and radiation-induced at a broad range of temperatures. Given that most published efforts have emphasized relatively Earth-like conditions, we can expect significant and enlightening discoveries as emphasis moves to the exotic atmospheres of exoplanets., Comment: Submitted as an Astro2020 Science White Paper

Rotationally resolved spectra of the C$^2\Sigma^+$-X$^2\Pi$ electronic system of the CH radical were measured using cavity ring-down spectroscopy in supersonically expanding, planar hydrocarbon plasma. The experimental conditions allowed the study of highly excited rotational levels starting from vibrationally excited states. Here we present some 200+ new or more accurately recorded transitions in the 0-0, 1-1 and 2-2 vibronic bands in the ultraviolet between 30900-32400 cm$^{-1}$ (324-309 nm). The resulting data, compared to earlier measurements, allows for the determination of more precise molecular constants for each vibrational state and therefore more precise equilibrium values. From this an equilibrium bond length of 1.115798(17) \r{A} for the C$^2{\Sigma}^+$ state is determined. A comprehensive list with observed transitions for each band has been compiled from all available experimental studies and constraints are placed on the predissociation lifetimes.

The fullerene C$_{60}$, one of the largest molecules identified in the interstellar medium (ISM), has been proposed to form top-down through the photo-chemical processing of large (more than 60 C-atoms) polycyclic aromatic hydrocarbon (PAH) molecules. In this article, we focus on the opposite process, investigating the possibility that fullerenes form from small PAHs, in which bowl-forming plays a central role. We combine laboratory experiments and quantum chemical calculations to study the formation of larger PAHs from charged fluorene clusters. The experiments show that with visible laser irradiation, the fluorene dimer cation - [C$_{13}$H$_{9}$$-$C$_{13}$H$_{9}$]$^+$ - and the fluorene trimer cation - [C$_{13}$H$_{9}$$-$C$_{13}$H$_{8}$$-$C$_{13}$H$_{9}$]$^+$ - undergo photo-dehydrogenation and photo-isomerization resulting in bowl structured aromatic cluster-ions, C$_{26}$H$_{12}$$^+$ and C$_{39}$H$_{20}$$^+$, respectively. To study the details of this chemical process, we employ quantum chemistry that allows us to determine the structures of the newly formed cluster-ions, to calculate the hydrogen loss dissociation energies, and to derive the underlying reaction pathways. These results demonstrate that smaller PAH clusters (with less than 60 C-atoms) can convert to larger bowled geometries that might act as building blocks for fullerenes, as the bowl-forming mechanism greatly facilitates the conversion from dehydrogenated PAHs to cages. Moreover, the bowl-forming induces a permanent dipole moment that - in principle - allows to search for such species using radio astronomy., Comment: 8 pages, 7 figures, accepted

We report cosmic ray ionization rates towards ten reddened stars studied within the framework of the EDIBLES (ESO Diffuse Interstellar Bands Large Exploration Survey) program, using the VLT-UVES. For each sightline, between 2 and 10 individual rotational lines of OH$^+$ have been detected in its (0,0) and (1,0) $A^3\Pi-X^3\Sigma^-$ electronic band system. This allows constraining of OH$^+$ column densities towards different objects. Results are also presented for 28 additional sightlines for which only one or rather weak signals are found. An analysis of these data makes it possible to derive the primary cosmic ray ionization rate $\zeta_p$ in the targeted diffuse interstellar clouds. For the ten selected targets, we obtain a range of values for $\zeta_p$ equal to $(3.9-16.4) \times 10^{-16}~\mathrm{s}^{-1}$. These values are higher than the numbers derived in previous detections of interstellar OH$^+$ in the far-infrared / sub-millimeter-wave regions and in other near-ultraviolet studies. This difference is a result of using new OH$^+$ oscillator strength values and a more complete picture of all relevant OH$^+$ formation and destruction routes (including the effect of proton recombinations on PAHs), and the relatively high $N$(OH$^+$) seen toward those ten targets.

We present a combined experimental and theoretical study of the photodissociation of the bisanthenequinone (C28H12O2) cation, Bq+. The experiments show that, upon photolysis, the Bq+ cation does not dehydrogenate, but instead fragments through the sequential loss of the two neutral carbonyl groups, causing the formation of five-membered carbon cycles. Quantum chemical calculations confirm this Bq+ -> [Bq - CO]+ -> [Bq - 2CO]+ sequence as the energetically most favorable reaction pathway. For the first CO loss, a transition state with a barrier of ~3.2 eV is found, substantially lower than the lowest calculated H loss dissociation pathway (~ 4.9 eV). A similar situation applies for the second CO loss channel (~3.8 eV vs. ~4.7 eV), but where the first dissociation step does not strongly alter the planar PAH geometry, the second step transforms the molecule into a bowl-shaped one.

The first gas-phase infrared spectra of two isolated astronomically relevant and large PAH cations - diindenoperylene (DIP) and dicoronylene (DC) - in the 530$-$1800 cm$^{-1}$ (18.9$-$5.6 $\mu$m) range - are presented. Vibrational band positions are determined for comparison to the aromatic infrared bands (AIBs). The spectra are obtained via infrared multiphoton dissociation (IRMPD) spectroscopy of ions stored in a quadrupole ion trap (QIT) using the intense and tunable radiation of the free electron laser for infrared experiments (FELIX). DIP$^{+}$ shows its main absorption peaks at 737 (13.57), 800 (12.50), 1001 (9.99), 1070 (9.35), 1115 (8.97), 1152 (8.68), 1278 (7.83), 1420 (7.04) and 1550 (6.45) cm$^{-1}$($\mu$m), in good agreement with DFT calculations that are uniformly scaled to take anharmonicities into account. DC$^+$ has its main absorption peaks at 853 (11.72), 876 (11.42), 1032 (9.69), 1168 (8.56), 1300 (7.69), 1427 (7.01) and 1566 (6.39) cm$^{-1}$($\mu$m), that also agree well with the scaled DFT results presented here. The DIP$^+$ and DC$^+$ spectra are compared with the prominent infrared features observed towards NGC 7023. This results both in matches and clear deviations. Moreover, in the 11.0$-$14.0 $\mu$m region, specific bands can be linked to CH out-of-plane (oop) bending modes of different CH edge structures in large PAHs. The molecular origin of these findings and their astronomical relevance are discussed.

We present the first infrared (IR) gas phase spectrum of a large and astronomically relevant PAH cation (C$_{42}$H$_{18}$$^+$, HBC$^+$) and its di-cation (C$_{42}$H$_{18}$$^{2+}$, HBC$^{2+}$). The spectra are recorded via infrared multi-photon dissociation (IRMPD) spectroscopy of ions stored in a quadrupole ion trap, using the intense infrared radiation of a free electron laser in the 530$-$1800 cm$^{-1}$ (5.6$-$18.9 $\mu$m) range. HBC$^{+}$ shows main intense absorption peaks at 762 (13.12), 1060 (9.43), 1192 (8.39), 1280 (7.81), 1379 (7.25) and 1530 (6.54) cm$^{-1}$($\mu$m), in good agreement with DFT calculations that after scaling to take the anharmonicities effect into account. HBC$^{2+}$ has its main absorption peaks at 660 (15.15), 766 (13.05), 1054 (9.49), 1176 (8.50), 1290 (7.75), 1370 (7.30) and 1530 (6.54) cm$^{-1}$($\mu$m). Given the similarity in the cationic and di-cationic spectra, we have not identified an obvious diagnostic signature to the presence of multiply charged PAHs in space. While experimental issues associated with the IRMPD technique preclude a detailed comparison with interstellar spectra, we do note that the strong bands of HBC$^+$ and HBC$^{2+}$ at $\sim$ 6.5, 7.7, 8.4 and 13.1 $\mu$m coincide with prominent aromatic infrared bands (AIBs). HBC has only trio CH groups and the out-of-plane CH bending mode of both HBC cations is measured at 13.1 $\mu$m, squarely in the range predicted by theory and previously found in studies of small (substituted) PAHs. This study therefore supports the use of AIBs observed in the 11$-$14 $\mu$m range as a diagnostic tool for the edge topology of large PAHs in space.

We present the first results of a pilot program to conduct an ALMA Band 10 spectral line survey of the high-mass star-forming region NGC 6334I. The observations were taken in exceptional weather conditions (0.19 mm precipitable water) with typical system temperatures $T_{\rm{sys}}$ $<$950 K at $\sim$890 GHz. A bright, bipolar north-south outflow is seen in HDO and CS emission, driven by the embedded massive protostar MM1B. This has allowed, for the first time, a direct comparison of the thermal water in this outflow to the location of water maser emission from prior 22 GHz VLA observations. The maser locations are shown to correspond to the sites along the outflow cavity walls where high velocity gas impacts the surrounding material. We also compare our new observations to prior Herschel HIFI spectral line survey data of this field, detecting an order of magnitude more spectral lines (695 vs 65) in the ALMA data. We focus on the strong detections of the complex organic molecule glycolaldehyde (HC(O)CH$_2$OH) in the ALMA data that is not detected in the heavily beam-diluted HIFI spectra. Finally, we stress the need for dedicated THz laboratory spectroscopy to support and exploit future high-frequency molecular line observations with ALMA., Comment: Accepted in ApJ Letters

The carriers of the diffuse interstellar bands (DIBs) are largely unidentified molecules ubiquitously present in the interstellar medium (ISM). After decades of study, two strong and possibly three weak near-infrared DIBs have recently been attributed to the C60+ fullerene based on observational and laboratory measurements. There is great promise for the identification of the over 400 other known DIBs, as this result could provide chemical hints towards other possible carriers. In an effort to systematically study the properties of the DIB carriers, we have initiated a new large-scale observational survey: the ESO Diffuse Interstellar Bands Large Exploration Survey (EDIBLES). The main objective is to build on and extend existing DIB surveys to make a major step forward in characterising the physical and chemical conditions for a statistically significant sample of interstellar lines-of-sight, with the goal to reverse-engineer key molecular properties of the DIB carriers. EDIBLES is a filler Large Programme using the Ultraviolet and Visual Echelle Spectrograph at the Very Large Telescope at Paranal, Chile. It is designed to provide an observationally unbiased view of the presence and behaviour of the DIBs towards early-spectral-type stars whose lines-of-sight probe the diffuse-to-translucent ISM. Such a complete dataset will provide a deep census of the atomic and molecular content, physical conditions, chemical abundances and elemental depletion levels for each sightline. Achieving these goals requires a homogeneous set of high-quality data in terms of resolution (R ~ 70000 -- 100000), sensitivity (S/N up to 1000 per resolution element), and spectral coverage (305--1042 nm), as well as a large sample size (100+ sightlines). In this first paper the goals, objectives and methodology of the EDIBLES programme are described and an initial assessment of the data is provided., Comment: 29 pages (including 14 pages appendix), 15 figures, accepted by A&A

In 2015, Campbell et al. (Nature 523, 322) presented spectroscopic laboratory gas phase data for the fullerene cation, C$_{60}^+$, that coincide with reported astronomical spectra of two diffuse interstellar band (DIB) features at 9633 and 9578 \AA. In the following year additional laboratory spectra were linked to three other and weaker DIBs at 9428, 9366, and 9349 \AA. The laboratory data were obtained using wavelength-dependent photodissociation spectroscopy of small (up to three) He-tagged C$_{60}^+-$He$_n$ ion complexes, yielding rest wavelengths for the bare C$_{60}^+$ cation by correcting for the He-induced wavelength shifts. Here we present an alternative approach to derive the rest wavelengths of the four most prominent C$_{60}^+$ absorption features, using high resolution laser dissociation spectroscopy of C$_{60}^+$ embedded in ultracold He droplets. Accurate wavelengths of the bare fullerene cation are derived based on linear wavelength shifts recorded for He$_n$C$_{60}^+$ species with $n$ up to 32. A careful analysis of all available data results in precise rest wavelengths (in air) for the four most prominent C$_{60}^+$ bands: 9631.9(1) \AA, 9576.7(1) \AA, 9427.5(1) \AA, and 9364.9(1) \AA. The corresponding band widths have been derived and the relative band intensity ratios are discussed.

Observational studies reveal that complex organic molecules (COMs) can be found in various objects associated with different star formation stages. The identification of COMs in prestellar cores, i.e., cold environments in which thermally induced chemistry can be excluded and radiolysis is limited by cosmic rays and cosmic ray induced UV-photons, is particularly important as this stage sets up the initial chemical composition from which ultimately stars and planets evolve. Recent laboratory results demonstrate that molecules as complex as glycolaldehyde and ethylene glycol are efficiently formed on icy dust grains via non-energetic atom addition reactions between accreting H atoms and CO molecules, a process that dominates surface chemistry during the 'CO-freeze out stage' in dense cores. In the present study we demonstrate that a similar mechanism results in the formation of the biologically relevant molecule glycerol - HOCH2CH(OH)CH2OH - a three-carbon bearing sugar alcohol necessary for the formation of membranes of modern living cells and organelles. Our experimental results are fully consistent with a suggested reaction scheme in which glycerol is formed along a chain of radical-radical and radical-molecule interactions between various reactive intermediates produced upon hydrogenation of CO ice or its hydrogenation products. The tentative identification of the chemically related simple sugar glyceraldehyde - HOCH2CH(OH)CHO - is discussed as well. These new laboratory findings indicate that the proposed reaction mechanism holds much potential to form even more complex sugar alcohols and simple sugars., Comment: Accepted for publication in The Astrophysical Journal

This study focuses on the formation of two molecules of astrobiological importance - glycolaldehyde (HC(O)CH2OH) and ethylene glycol (H2C(OH)CH2OH) - by surface hydrogenation of CO molecules. Our experiments aim at simulating the CO freeze-out stage in interstellar dark cloud regions, well before thermal and energetic processing become dominant. It is shown that along with the formation of H2CO and CH3OH - two well established products of CO hydrogenation - also molecules with more than one carbon atom form. The key step in this process is believed to be the recombination of two HCO radicals followed by the formation of a C-C bond. The experimentally established reaction pathways are implemented into a continuous-time random-walk Monte Carlo model, previously used to model the formation of CH3OH on astrochemical time-scales, to study their impact on the solid-state abundances in dense interstellar clouds of glycolaldehyde and ethylene glycol.

The surface formation of NH3 and its deuterated isotopologues - NH2D, NHD2, and ND3 - is investigated at low temperatures through the simultaneous addition of hydrogen and deuterium atoms to nitrogen atoms in CO-rich interstellar ice analogues. The formation of all four ammonia isotopologues is only observed up to 15 K, and drops below the detection limit for higher temperatures. Differences between hydrogenation and deuteration yields result in a clear deviation from a statistical distribution in favour of deuterium enriched species. The data analysis suggests that this is due to a higher sticking probability of D atoms to the cold surface, a property that may generally apply to molecules that are formed in low temperature surface reactions. The results found here are used to interpret ammonia deuterium fractionation as observed in pre-protostellar cores.

Solid state astrochemical reaction pathways have the potential to link the formation of small nitrogen-bearing species, like NH3 and HNCO, and prebiotic molecules, specifically amino acids. To date, the chemical origin of such small nitrogen containing species is still not well understood, despite the fact that ammonia is an abundant constituent of interstellar ices toward young stellar objects and quiescent molecular clouds. This is mainly because of the lack of dedicated laboratory studies. The aim of the present work is to experimentally investigate the formation routes of NH3 and HNCO through non-energetic surface reactions in interstellar ice analogues under fully controlled laboratory conditions and at astrochemically relevant temperatures. This study focuses on the formation of NH3 and HNCO in CO-rich (non-polar) interstellar ices that simulate the CO freeze-out stage in dark interstellar cloud regions, well before thermal and energetic processing start to become relevant. We demonstrate and discuss the surface formation of solid HNCO through the interaction of CO molecules with NH radicals - one of the intermediates in the formation of solid NH3 upon sequential hydrogenation of N atoms. The importance of HNCO for astrobiology is discussed.

Hydroxylamine (NH2OH) is one of the potential precursors of complex pre-biotic species in space. Here we present a detailed experimental study of hydroxylamine formation through nitric oxide (NO) surface hydrogenation for astronomically relevant conditions. The aim of this work is to investigate hydroxylamine formation efficiencies in polar (water-rich) and non-polar (carbon monoxide-rich) interstellar ice analogues. A complex reaction network involving both final (N2O, NH2OH) and intermediate (HNO, NH2O, etc.) products is discussed. The main conclusion is that hydroxylamine formation takes place via a fast and barrierless mechanism and it is found to be even more abundantly formed in a water-rich environment at lower temperatures. In parallel, we experimentally verify the non-formation of hydroxylamine upon UV photolysis of NO ice at cryogenic temperatures as well as the non-detection of NC- and NCO-bond bearing species after UV processing of NO in carbon monoxide-rich ices. Our results are implemented into an astrochemical reaction model, which shows that NH2OH is abundant in the solid phase under dark molecular cloud conditions. Once NH2OH desorbs from the ice grains, it becomes available to form more complex species (e.g., glycine and beta-alanine) in gas phase reaction schemes.

The laboratory work presented here, simulates the chemistry on icy dust grains as typical for the 'CO freeze-out stage' in dark molecular clouds. It differs from previous studies in that solid-state hydrogenation and vacuum UV-photoprocessing are applied simultaneously to co-depositing molecules. In parallel, the reactions at play are described for fully characterized laboratory conditions. The focus is on the formation of molecules containing both carbon and nitrogen atoms, starting with NO in CO-, H2CO-, and CH3OH-rich ices at 13 K. The experiments yield three important conclusions. 1. Without UV-processing hydroxylamine (NH2OH) is formed, as reported previously. 2. With UV-processing (energetic) NH2 is formed through photodissociation of NH2OH. This radical is key in the formation of species with an N-C bond. 3. The formation of three N-C bearing species, HNCO, OCN- and NH2CHO is observed. The experiments put a clear chemical link between these species; OCN- is found to be a direct derivative of HNCO and the latter is shown to have the same precursor as formamide (NH2CHO). Moreover, the addition of VUV competing channels decreases the amount of NO molecules converted into NH2OH by at least one order of magnitude. Consequently, this decrease in NH2OH formation yield directly influences the amount of NO molecules that can be converted into HNCO, OCN- and NH2CHO.

We present a combined experimental and theoretical study focussing on the quantum tunneling of atoms in the reaction between CH4 and OH. The importance of this reaction pathway is derived by investigating isotope substituted analogs. Quantitative reaction rates needed for astrochemical models at low temperature are currently unavailable both in the solid state and in the gas phase. Here, we study tunneling effects upon hydrogen abstraction in CH4 + OH by focusing on two reactions: CH4 + OD -> CH3 + HDO and CD4 + OH -> CD3 + HDO. The experimental study shows that the solid-state reaction rate R(CH4 + OD) is higher than R(CD4 + OH) at 15 K. Experimental results are accompanied by calculations of the corresponding unimolecular and bimolecular reaction rate constants using instanton theory taking into account surface effects. From the work presented here, the unimolecular reactions are particularly interesting as these provide insight into reactions following a Langmuir-Hinshelwood process. The resulting ratio of the rate constants shows that the H abstraction (k(CH4 + OD)) is approximately ten times faster than D-abstraction (k(CD4 + OH)) at 65 K. We conclude that tunneling is involved at low temperatures in the abstraction reactions studied here. The unimolecular rate constants can be used by the modeling community as a first approach to describe OH-mediated abstraction reactions in the solid phase. For this reason we provide fits of our calculated rate constants that allow the inclusion of these reactions in models in a straightforward fashion., Comment: Accepted by A&A

Electronic spectra of C$_6$H are measured in the $18\,950-21\,100$ cm$^{-1}$ domain using cavity ring-down spectroscopy of a supersonically expanding hydrocarbon plasma. In total, 19 (sub)bands of C$_6$H are presented, all probing the vibrational manifold of the B$^2\Pi$ electronically excited state. The assignments are guided by electronic spectra available from matrix isolation work, isotopic substitution experiments (yielding also spectra for $^{13}$C$_6$H and C$_6$D), predictions from ab initio calculations as well as rotational fitting and vibrational contour simulations using the available ground state parameters as obtained from microwave experiments. Besides the $0_0^0$ origin band, three non-degenerate stretching vibrations along the linear backbone of the C$_6$H molecule are assigned: the $\nu_6$ mode associated with the C-C bond vibration and the $\nu_4$ and $\nu_3$ modes associated with C$\equiv$C triple bonds. For the two lowest $\nu_{11}$ and $\nu_{10}$ bending modes, a Renner-Teller analysis is performed identifying the $\mu^2\Sigma$($\nu_{11}$) and both $\mu^2\Sigma$($\nu_{10}$) and $\kappa^2\Sigma$($\nu_{10}$) components. In addition, two higher lying bending modes are observed, which are tentatively assigned as $\mu^2\Sigma$($\nu_9$) and $\mu^2\Sigma$($\nu_8$) levels. In the excitation region below the first non-degenerate vibration ($\nu_6$), some $^2\Pi-^{2}\Pi$ transitions are observed that are assigned as even combination modes of low-lying bending vibrations. The same holds for a $^2\Pi-^{2}\Pi$ transition found above the $\nu_6$ level. From these spectroscopic data and the vibronic analysis a comprehensive energy level diagram for the B$^2\Pi$ state of C$_6$H is derived and presented., Comment: Accepted for publication in The Journal of Physical Chemistry A (26 July 2016)

Wavelength dependent photodesorption rates have been determined using synchrotron radiation, for condensed pure and mixed methanol ice in the 7 -- 14 eV range. The VUV photodesorption of intact methanol molecules from pure methanol ices is found to be of the order of 10$^{-5}$ molecules/photon, that is two orders of magnitude below what is generally used in astrochemical models. This rate gets even lower ($<$ 10$^{-6}$ molecules/photon) when the methanol is mixed with CO molecules in the ices. This is consistent with a picture in which photodissociation and recombination processes are at the origin of intact methanol desorption from pure CH$_3$OH ices. Such low rates are explained by the fact that the overall photodesorption process is dominated by the desorption of the photofragments CO, CH$_3$, OH, H$_2$CO and CH$_3$O/CH$_2$OH, whose photodesorption rates are given in this study. Our results suggest that the role of the photodesorption as a mechanism to explain the observed gas phase abundances of methanol in cold media is probably overestimated. Nevertheless, the photodesorption of radicals from methanol-rich ices may stand at the origin of the gas phase presence of radicals such as CH$_3$O, therefore opening new gas phase chemical routes for the formation of complex molecules., Comment: 13 pages, 2 figures, 1 table