arXiv subjects

Harold Linnartz

Publications and source records attributed to Harold Linnartz.

At least 19 recordsLinked to original sources

arXiv2024

Formation of carbonyl sulfide (OCS) via SH radicals in interstellar CO-rich ice under dense cloud conditions

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.

astro-ph.GA↗

arXiv2024

Formation of S-bearing complex organic molecules in interstellar clouds via ice reactions with C2H2, HS, and atomic H

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.

astro-ph.GA↗

arXiv2024

JWST detections of amorphous and crystalline HDO ice toward massive protostars

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.

astro-ph.SR↗

arXiv2024

JWST observations of $^{13}$CO$_{2}$ ice: Tracing the chemical environment and thermal history of ices in protostellar envelopes

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.

astro-ph.GA↗

arXiv2024

JWST Observations of Young protoStars (JOYS): Linked accretion and ejection in a Class I protobinary system

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.

astro-ph.SR↗

arXiv2023

The EDIBLES Survey. VII. A survey of C2 and C3 in interstellar clouds

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.

astro-ph.GA↗

arXiv2023

The EDIBLES survey VI. Searching for time variations of interstellar absorption features

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.

astro-ph.GA↗

arXiv2023

Interaction of H$_2$S with H atoms on grain surfaces under molecular cloud conditions

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.

astro-ph.GA↗

arXiv2023

The hunt for formamide in interstellar ices: A toolkit of laboratory infrared spectra in astronomically relevant ice mixtures and comparisons to ISO, Spitzer, and JWST observations

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.

astro-ph.GA↗

arXiv2023

The Bending of C$_3$: Experimentally Probing the $l$-type Doubling and Resonance

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 ($ν_2$) 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 $^1Π_u -$ X $^1Σ_g^+$) 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 $ν_3$ 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 $ν_2$. 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 $ν_2$ 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.

astro-ph.GA↗

arXiv2022

Infrared spectra of complex organic molecules in astronomically relevant ice mixtures. V. Methyl cyanide (acetonitrile)

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$μ$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.

astro-ph.GA↗

arXiv2022

First experimental confirmation of the CH3O + H2CO -> CH3OH + HCO reaction: expanding the CH3OH formation mechanism in interstellar ices

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.

astro-ph.GA↗

arXiv2022

The EDIBLES survey V: Line profile variations in the $λλ$5797, 6379, and 6614 diffuse interstellar bands as a tool to constrain carrier sizes

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 $λλ$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 $λ$6614 DIB carrier and assuming a linear carrier, we found B$_{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 ($λ$6614 carrier, linear) to 77--114 carbon atoms ($λ$6379, spherical).

astro-ph.GA↗

arXiv2022

The prebiotic molecular inventory of Serpens SMM1: II. The building blocks of peptide chains

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 $ν_{12}$=1, NH$_{2}^{13}$CHO, CH$_{3}$C(O)NH$_{2}$ $ν$=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 $ν$=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.

astro-ph.GA↗

arXiv2022

Thermal desorption of interstellar ices. A review on the controlling parameters and their implications fromsnowlines to chemical complexity

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.

astro-ph.GA↗

arXiv2021

Methoxymethanol Formation Starting from CO-Hydrogenation

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.

astro-ph.GA↗

arXiv2021

Refractive index and extinction coefficient of vapor-deposited water ice in the UV-Vis range

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 $μ$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.

astro-ph.IM↗

arXiv2021

Hydrogenation of accreting C-atoms and CO molecules -- simulating ketene and acetaldehyde formation under dark and translucent cloud conditions

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.

astro-ph.GA↗