arXiv subjects

H. Linnartz

Publications and source records attributed to H. Linnartz.

At least 37 records · Page 2Linked to original sources

arXiv2022

LIDA - The Leiden Ice Database for Astrochemistry

High quality vibrational spectra of solid-phase molecules in ice mixtures and for temperatures of astrophysical relevance are needed to interpret infrared observations toward protostars and background stars. Over the last 25 years, the Laboratory for Astrophysics at Leiden Observatory has provided more than 1100 spectra of diverse ice samples. Timely with the recent launch of the James Webb Space Telescope, we have fully upgraded the Leiden Ice Database for Astrochemistry (LIDA) adding recently measured spectra. The goal of this manuscript is to describe what options exist to get access to and work with a large collection of IR spectra, and the UV/vis to mid-infrared refractive index of H2O ice and astronomy-oriented online tools to support the interpretation of IR ice observations. LIDA uses Flask and Bokeh for generating the web pages and graph visualization, respectively, SQL for searching ice analogues within the database and Jmol for 3D molecule visualization. The infrared data in the database are recorded via transmission spectroscopy of ice films condensed on cryogenic substrates. The real UV/vis refractive indices of H2O ice are derived from interference fringes created from the simultaneous use of a monochromatic HeNe laser beam and a broadband Xe-arc lamp, whereas the real and imaginary mid-IR values are theoretically calculated. LIDA also offers online tools. The first tool, SPECFY, used to create a synthetic spectrum of ices towards protostars. The second tool aims at the calculation of mid-infrared refractive index values. LIDA allows to search, download and visualize experimental data of astrophysically relevant molecules in the solid phase, as well as to provide the means to support astronomical observations. As an example, we analyse the spectrum of the protostar AFGL 989 using the resources available in LIDA and derive the column densities of H2O, CO and CO2 ices.

astro-ph.IM↗

arXiv2022

Reconciling spectroscopy with dynamics in global potential energy surfaces: the case of the astrophysically relevant SiC$_{2}$

SiC$_2$ is a fascinating molecule due to its unusual bonding and astrophysical importance. In this work, we report the first global potential energy surface (PES) for ground-state SiC$_2$ using the combined-hyperbolic-inverse-power-representation (CHIPR) method and accurate ab initio energies. The calibration grid data is obtained via a general dual-level protocol developed afresh herein that entails both coupled-cluster and multireference configuration interaction energies jointly extrapolated to the complete basis set limit. Such an approach is specially devised to recover much of the spectroscopy from the PES, while still permitting a proper fragmentation of the system to allow for reaction dynamics studies. Besides describing accurately the valence strongly-bound region that includes both the cyclic global minimum and isomerization barriers, the final analytic PES form is shown to properly reproduce dissociation energies, diatomic potentials, and long-range interactions at all asymptotic channels, in addition to naturally reflect the correct permutational symmetry of the potential. Bound vibrational state calculations have been carried out, unveiling an excellent match of the available experimental data on $c$-$\mathrm{SiC}_{2}(^{1}A_1)$. To further exploit the global nature of the PES, exploratory quasi-classical trajectory calculations for the endothermic $\mathrm{C_{2}\!+\!Si}\rightarrow\mathrm{SiC\!+\!C}$ reaction are also performed, yielding thermalized rate coefficients for temperatures up to $5000$ K. The results hint for the prominence of this reaction in the innermost layers of the circumstellar envelopes around carbon-rich stars, thence conceivably playing therein a key contribution to the gas-phase formation of SiC, and eventually, solid SiC dust.

physics.chem-ph↗

arXiv2022

CRIRES high-resolution near-infrared spectroscopy of diffuse interstellar band profiles. Detection of 12 new DIBs in the YJ band and the introduction of a combined ISM sight line and stellar analysis approach

A high spectral resolution investigation of diffuse interstellar bands (DIBs) in the near-infrared ($YJ$ band) is conducted to test new methods, to confirm and improve existing parameters, and to search for new DIBs. Methods: The CRyogenic high-resolution InfraRed Echelle Spectrograph (CRIRES) on the European Southern Observatory's Very Large Telescope was employed to obtain spectra of four reddened background supergiant stars (HD 183143, HD 165784, HD 92207, HD 111613) and an unreddened comparison star (HD 87737) at the highest resolution of $R \approx 100000$ currently achievable at near-infrared wavelengths. The correction for telluric absorption was performed by a modelling approach. Non-local thermodynamic equilibrium spectral modelling of available optical and the new near-infrared spectra facilitated a comprehensive characterisation of the atmospheric properties of the background stars. A more precise and accurate determination of the reddening law along the sight lines could be achieved than feasible before by comparison of the observed and model spectral energy distributions. For DIBs that overlap with stellar lines the DIB profile shapes could be recovered. Results: Seventeen known near-infrared DIBs were confirmed, and 12 previously unknown and generally weaker DIBs were identified in the $YJ$ band. Three DIBs that show uniform profiles along all sight lines were identified, possibly connected to transitions from a common lower state of the same carrier. The divergent extinction curve towards the frequently discussed DIB standard star HD 183143 could be reproduced for the first time, requiring extra absorption by $\sim$3.5 mag due to polycyclic aromatic hydrocarbons (PAHs) to match the ultraviolet extinction bump. This extra absorption probably stems from a circumstellar bubble lying in front of the star which is intersected tangentially by the line of sight.

astro-ph.GA↗

arXiv2021

High-level ab initio quartic force fields and spectroscopic characterization of C$_{2}$N$^{-}$

While it is now well established that large carbon chain species and radiative electron attachment (REA) are key ingredients triggering interstellar anion chemistry, the role played by smaller molecular anions, for which REA appears to be an unlikely formation pathway, is as yet elusive. Advancing this research undoubtedly requires the knowledge of their astronomical abundances which, for the case of C$_{2}$N$^{-}$, is largely hindered by a lack of accurate spectroscopic signatures. In this work, we provide such data for both ground $\ell$-CCN$^{-}$($^{3}Σ^{-}$) and low-lying $c$-CNC$^{-}$($^{1}A_{1}$) isomers by means of state-of-the-art rovibrational quantum chemical techniques. Their quartic force fields are herein calibrated using a high-level composite energy scheme that accounts for extrapolations to both one-particle and (approximate) ${N}$-particle basis set limits, in addition to relativistic effects, with the final forms being subsequently subject to nuclear motion calculations. Besides standard spectroscopic attributes, the full set of computed properties includes fine and hyperfine interaction constants and can be readily introduced as guesses in conventional experimental data reduction analyses through effective Hamiltonians. On the basis of benchmark calculations, the target accuracies are determined to be better than 0.1% of experiment for rotational constants and 0.3% for vibrational fundamentals. Apart from laboratory investigations, the results here presented are expected to also prompt future astronomical surveys on C$_{2}$N$^{-}$. Using the theoretically-predicted spectroscopic constants, the rotational spectra of both $\ell$-CCN$^{-}$($^{3}Σ^{-}$) and $c$-CNC$^{-}$($^{1}A_{1}$) are also derived and their likely detectability in the interstellar medium is further explored in connection with working frequency ranges of powerful astronomical facilities.

astro-ph.GA↗

arXiv2021

Formation of complex organic molecules in molecular clouds: acetaldehyde, vinyl alcohol, ketene, and ethanol via the "energetic" processing of C$_2$H$_2$ ice

The simultaneous detection of organic molecules of the form C$_2$H$_{\text{n}}$O, such as ketene (CH$_2$CO), acetaldehyde (CH$_3$CHO), and ethanol (CH$_3$CH$_2$OH), toward early star-forming regions offers hints of shared chemical history. Several reaction routes have been proposed and experimentally verified under various interstellar conditions to explain the formation pathways involved. Most noticeably, the non-energetic processing of C$_2$H$_2$ ice with OH-radicals and H-atoms was shown to provide formation routes to ketene, acetaldehyde, ethanol, and vinyl alcohol (CH$_2$CHOH) along the H$_2$O formation sequence on grain surfaces. In this work, the non-energetic formation scheme is extended with laboratory measurements focusing on the energetic counterpart, induced by cosmic rays penetrating the H$_2$O-rich ice mantle. The focus here is on the H$^+$ radiolysis of interstellar C$_2$H$_2$:H$_2$O ice analogs at 17 K. Ultra-high vacuum experiments were performed to investigate the 200 keV H$^+$ radiolysis chemistry of predeposited C$_2$H$_2$:H$_2$O ices, both as mixed and layered geometries. Fourier-transform infrared spectroscopy was used to monitor in situ newly formed species as a function of the accumulated energy dose (or H$^+$ fluence). The infrared (IR) spectral assignments are further confirmed in isotope labeling experiments using H$_2$$^{18}$O. The energetic processing of C$_2$H$_2$:H$_2$O ice not only results in the formation of (semi-) saturated hydrocarbons (C$_2$H$_4$ and C$_2$H$_6$) and polyynes as well as cumulenes (C$_4$H$_2$ and C$_4$H$_4$), but it also efficiently forms O-bearing COMs, including vinyl alcohol, ketene, acetaldehyde, and ethanol, for which the reaction cross-section and product composition are derived. A clear composition transition of the product, from H-poor to H-rich species, is observed as a function of the accumulated energy dose.

astro-ph.GA↗

arXiv2021

Complex organic molecules in low-mass protostars on Solar System scales -- II. Nitrogen-bearing species

The chemical inventory of planets is determined by the physical and chemical processes that govern the early phases of star formation. The aim is to investigate N-bearing complex organic molecules towards two Class 0 protostars (B1-c and S68N) at millimetre wavelengths with ALMA. Next, the results of the detected N-bearing species are compared with those of O-bearing species for the same and other sources. ALMA observations in Band 6 ($\sim$ 1 mm) and Band 5 ($\sim$ 2 mm) are studied at $\sim$ 0.5" resolution, complemented by Band 3 ($\sim$ 3 mm) data in a $\sim$ 2.5" beam. NH2CHO, C2H5CN, HNCO, HN13CO, DNCO, CH3CN, CH2DCN, and CHD2CN are identified towards the investigated sources. Their abundances relative to CH3OH and HNCO are similar for the two sources, with column densities that are typically an order of magnitude lower than those of O-bearing species. The largest variations, of an order of magnitude, are seen for NH2CHO abundance ratios with respect to HNCO and CH3OH and do not correlate with the protostellar luminosity. In addition, within uncertainties, the N-bearing species have similar excitation temperatures to those of O-bearing species ($\sim$ 100 $\sim$ 300 K). The similarity of most abundances with respect to HNCO, including those of CH2DCN and CHD2CN, hints at a shared chemical history, especially the high D/H ratio in cold regions prior to star formation. However, some of the variations in abundances may reflect the sensitivity of the chemistry to local conditions such as temperature (e.g. NH2CHO), while others may arise from differences in the emitting areas of the molecules linked to their different binding energies in the ice. The two sources discussed here add to the small number of sources with such a detailed chemical analysis on Solar System scales. Future JWST data will allow a direct comparison between the ice and gas abundances of N-bearing species.

astro-ph.GA↗

arXiv2021

Theoretical studies of carbon isotopic fractionation in reactions of C with C$_{2}$: dynamics, kinetics, and isotopologue equilibria

Our current understanding of interstellar carbon fractionation hinges on the interpretation of astrochemical kinetic models. Yet, the various reactions included carry large uncertainties in their (estimated) rate coefficients, notably those involving C with C$_{2}$. In this work, we provide theoretical thermal rate coefficients as a function of the temperature for all possible gas-phase isotope-exchange reactions of C+C$_{2}(X^{1}Σ_{g}^{+},a^{3}Π_{u})$. For this, we employ the quasi-classical trajectory method, with the previously obtained potential energy surfaces of C$_{3}$ dictating the forces between the colliding partners. The calculated rate coefficients show a positive temperature dependence and are markedly different from previous theoretical estimates. While the forward reactions are fast and inherently exothermic owing to the lower zero-point energy content of the products, the reverse processes have temperature thresholds. For each reaction considered, analytic three-parameter Arrhenius-Kooij formulas are provided that readily interpolate/extrapolate the associated forward and backward rates. These forms can further be introduced in astrochemical networks. Apart from the proper kinetic attributes, we also provide equilibrium constants for these processes, thence confirming their prominence in the overall C fractionation chemistry. In this respect, the $^{13}$C + $^{12}$C$_{2}(X^{1}Σ^{+}_{g})$ and $^{13}$C + $^{12}$C$_{2}(a^{3}Π_{u})$ reactions are found to be particularly conspicuous, notably at the typical temperatures of dense molecular clouds. For these reactions and considering both equilibrium and time-dependent chemistry, theoretical $^{12}$C/$^{13}$C ratios as a function of the gas kinetic temperature are also derived and shown to be consistent with available model chemistry and observational data on C$_{2}$

astro-ph.GA↗

arXiv2020

The prebiotic molecular inventory of Serpens SMM1 I. An investigation of the isomers CH$_{3}$NCO and HOCH$_{2}$CN

Methyl isocyanate (CH$_{3}$NCO) and glycolonitrile (HOCH$_{2}$CN) are isomers and prebiotic molecules that are involved in the formation of peptide structures and the nucleobase adenine, respectively. ALMA observations of the intermediate-mass Class 0 protostar Serpens SMM1-a and ALMA-PILS data of the low-mass Class 0 protostar IRAS~16293B are used. Spectra are analysed with the CASSIS line analysis software package in order to identify and characterise molecules. CH$_{3}$NCO, HOCH$_{2}$CN, and various other molecules are detected towards SMM1-a. HOCH$_{2}$CN is identified in the PILS data towards IRAS~16293B in a spectrum extracted at a half-beam offset position from the peak continuum. CH$_{3}$NCO and HOCH$_{2}$CN are equally abundant in SMM1-a at [X]/[CH$_{3}$OH] of 5.3$\times$10$^{-4}$ and 6.2$\times$10$^{-4}$, respectively. A comparison between SMM1-a and IRAS~16293B shows that HOCH$_{2}$CN and HNCO are more abundant in the former source, but CH$_{3}$NCO abundances do not differ significantly. Data from other sources are used to show that the [CH$_{3}$NCO]/[HNCO] ratio is similar in all these sources within $\sim$10\%. The new detections of CH$_{3}$NCO and HOCH$_{2}$CN are additional evidence for a large interstellar reservoir of prebiotic molecules that can contribute to the formation of biomolecules on terrestrial planets. A plausible formation pathway for HOCH$_{2}$CN is the thermal Strecker-like reaction of CN$^{-}$ with H$_{2}$CO. The similar [CH$_{3}$NCO]/[HNCO] ratios indicate that these two species either are chemically related or their formation is affected by physical conditions in the same way. The relatively high abundances of HOCH$_{2}$CN and HNCO in SMM1-a may be explained by a prolonged stage of relatively warm ice mantles, where thermal and energetic processing of HCN in the ice results in the efficient formation of both species.

astro-ph.SR↗

arXiv2020

A non-energetic mechanism for glycine formation in the interstellar medium

The detection of the amino acid glycine and its amine precursor methylamine on the comet 67P/Churyumov-Gerasimenko by the Rosetta mission provides strong evidence for a cosmic origin of prebiotics on Earth. How and when such complex organic molecules form along the process of star- and planet-formation remains debated. We report the first laboratory detection of glycine formed in the solid phase through atom and radical-radical addition surface reactions under cold dense interstellar cloud conditions. Our experiments, supported by astrochemical models, suggest that glycine forms without the need for energetic irradiation, such as UV photons and cosmic rays, in interstellar water-rich ices, where it remains preserved, in a much earlier star-formation stage than previously assumed. We also confirm that solid methylamine is an important side-reaction product. A prestellar formation of glycine on ice grains provides the basis for a complex and ubiquitous prebiotic chemistry in space enriching the chemical content of planet-forming material.

astro-ph.IM↗

arXiv2020

Complex organic molecules in low-mass protostars on solar system scales -- I. Oxygen-bearing species

Complex organic molecules (COMs) are thought to form on icy dust grains in the earliest phase of star formation. The evolution of these COMs from the youngest Class 0/I protostellar phases toward the more evolved Class II phase is still not fully understood. Since planet formation seems to start early, and mature disks are too cold for characteristic COM emission lines, studying the inventory of COMs on solar system scales in the Class 0/I stage is relevant. ALMA Band 3 (3 mm) and Band 6 (1 mm) observations are obtained of seven Class 0 protostars in the Perseus and Serpens star-forming regions. By modeling the inner protostellar region using 'LTE' models, the excitation temperature and column densities are determined for several O-bearing COMs. B1-c, B1-bS, and Serpens S68N show COM emission, i.e, three out of the seven sources. No clear correlation seems to exist between the occurrence of COMs and source luminosity. The abundances of several COMs with respect to CH3OH are remarkably similar for the three COM-rich sources, and to IRAS 16293-2422B and HH 212. For other COMs the abundances differ by up to an order of magnitude, indicating that local source conditions are case determining. B1-c hosts a cold ($T_{ex}\approx60$ K), more extended component of COM emission with a column density of typically a few % of the warm/hot ($T_{ex}\sim 200$ K), central component. A D/H ratio of 1-3 % is derived based on the CH2DOH/CH3OH ratio suggesting a temperature of $\sim$15~K during the formation of methanol. This ratio is consistent with other low-mass protostars. Future mid-infrared facilities such as JWST/MIRI will be essential to directly observe COM ices. Combining this with a larger sample of COM-rich sources with ALMA will allow for directly linking ice and gas-phase abundances in order to constrain the routes that produce and maintain chemical complexity during the star formation process.

astro-ph.SR↗

arXiv2020

A cryogenic ice setup to simulate carbon atom reactions in interstellar ices

The design, implementation, and performance of a customized carbon atom beam source for the purpose of investigating solid-state reaction routes in interstellar ices in molecular clouds are discussed. The source is integrated into an existing ultrahigh vacuum setup, SURFace REaction SImulation DEvice (SURFRESIDE$^{2}$), which extends this double atom (H/D, O, and N) beamline apparatus with a third atom (C) beamline to a unique system that is fully suited to explore complex organic molecule solid-state formation under representative interstellar cloud conditions. The parameter space for this system is discussed, which includes the flux of the carbon atoms hitting the ice sample, their temperature, and the potential impact of temperature on ice reactions. Much effort has been put into constraining the beam size to within the limits of the sample size with the aim to reduce carbon pollution inside the setup. How the C-atom beam performs is quantitatively studied through the example experiment, C + $^{18}$O$_2$, and supported by computationally-derived activation barriers. The potential for this source to study the solid-state formation of interstellar complex organic molecules through C-atom reactions is discussed.

astro-ph.SR↗

arXiv2020

An experimental study of the surface formation of methane in interstellar molecular clouds

Methane is one of the simplest stable molecules that is both abundant and widely distributed across space. It is thought to have partial origin from interstellar molecular clouds, which are near the beginning of the star formation cycle. Observational surveys of CH$_4$ ice towards low- and high-mass young stellar objects showed that much of the CH$_4$ is expected to be formed by the hydrogenation of C on dust grains, and that CH$_4$ ice is strongly correlated with solid H$_2$O. Yet, this has not been investigated under controlled laboratory conditions, as carbon-atom chemistry of interstellar ice analogues has not been experimentally realized. In this study, we successfully demonstrate with a C-atom beam implemented in an ultrahigh vacuum apparatus the formation of CH$_4$ ice in two separate co-deposition experiments: C + H on a 10 K surface to mimic CH$_4$ formation right before H$_2$O ice is formed on the dust grain, and C + H + H$_2$O on a 10 K surface to mimic CH$_4$ formed simultaneously with H$_2$O ice. We confirm that CH$_4$ can be formed by the reaction of atomic C and H, and that the CH$_4$ formation rate is 2 times greater when CH$_4$ is formed within a H$_2$O-rich ice. This is in agreement with the observational finding that interstellar CH$_4$ and H$_2$O form together in the polar ice phase, i.e., when C- and H-atoms simultaneously accrete with O-atoms on dust grains. For the first time, the conditions that lead to interstellar CH$_4$ (and CD$_4$) ice formation are reported, and can be incorporated into astrochemical models to further constrain CH$_4$ chemistry in the interstellar medium and in other regions where CH$_4$ is inherited.

astro-ph.SR↗

arXiv2020

Deep search for hydrogen peroxide toward pre- and protostellar objects -- Testing the pathway of grain surface water formation

Context: In the laboratory, hydrogen peroxide (HOOH) was proven to be an intermediate product in the solid-state reaction scheme that leads to the formation of water on icy dust grains. When HOOH desorbs from the icy grains, it can be detected in the gas phase. In combination with water detections, it may provide additional information on the water reaction network. Hydrogen peroxide has previously been found toward $ρ$ Oph A. However, further searches for this molecule in other sources failed. Hydrogen peroxide plays a fundamental role in the understanding of solid-state water formation and the overall water reservoir in young stellar objects (YSOs). Without further HOOH detections, it is difficult to assess and develop suitable chemical models that properly take into account the formation of water on icy surfaces. Aims: The objective of this work is to identify HOOH in YSOs and thereby constrain the grain surface water formation hypothesis. Methods: Using an astrochemical model based on previous work in combination with a physical model of YSOs, the sources R CrA-IRS\,5A, NGCC1333-IRAS\,2A, L1551-IRS\,5, and L1544 were identified as suitable candidates for an HOOH detection. Long integration times on the APEX 12m and IRAM 30m telescopes were applied to search for HOOH signatures in these sources. Results: None of the four sources under investigation showed convincing spectral signatures of HOOH. The upper limit for HOOH abundance based on the noise level at the frequency positions of this molecule for the source R CrA-IRS\,5A was close to the predicted value. For NGC1333-IRAS 2A, L1544, and L1551-IRS\,5, the model overestimated the hydrogen peroxide abundances.

astro-ph.SR↗

arXiv2020

Formation of complex molecules in translucent clouds: Acetaldehyde, vinyl alcohol, ketene, and ethanol via nonenergetic processing of C2H2 ice

Complex organic molecules (COMs) have been identified toward high- and low-mass protostars as well as molecular clouds, suggesting that these interstellar species originate from the early stage(s) of starformation. The reaction pathways resulting in COMs described by the formula C$_2$H$_\text{n}$O are still under debate. In this work, we investigate the laboratory possible solid-state reactions that involve simple hydrocarbons and OH-radicals along with H$_2$O ice under translucent cloud conditions (1$\leq$A$_V$$\leq$5 and \textit{n}$_\text{H}$$\sim$10$^3$ cm$^{-3}$). We focus on the interactions of C$_2$H$_2$ with H-atoms and OH-radicals, which are produced along the H$_2$O formation sequence on grain surfaces at 10 K. Ultra-high vacuum (UHV) experiments were performed to study the surface chemistry observed during C$_2$H$_2$ + O$_2$ + H codeposition, where O$_2$ was used for the in-situ generation of OH-radicals. Reflection absorption infrared spectroscopy (RAIRS) was applied to in situ monitor the initial and newly formed species. After that, a temperature-programmed desorption experiment combined with a Quadrupole mass spectrometer (TPD-QMS) was used as a complementary analytical tool. The investigated 10 K surface chemistry of C$_2$H$_2$ with H-atoms and OH-radicals not only results in semi and fully saturated hydrocarbons, such as ethylene (C$_2$H$_4$) and ethane (C$_2$H$_6$), but it also leads to the formation of COMs, such as vinyl alcohol, acetaldehyde, ketene, ethanol, and possibly acetic acid. It is concluded that OH-radical addition reactions to C$_2$H$_2$, acting as a molecular backbone, followed by isomerization (i.e., keto-enol tautomerization) via an intermolecular pathway and successive hydrogenation provides a so far experimentally unreported solid-state route for the formation of these species without the need of energetic input.

astro-ph.SR↗

arXiv2019

Synthesis of solid-state Complex Organic Molecules through accretion of simple species at low temperatures

Complex organic molecules (COMs) have been detected in the gas-phase in cold and lightless molecular cores. Recent solid-state laboratory experiments have provided strong evidence that COMs can be formed on icy grains through 'non-energetic' processes. In this contribution, we show that propanal and 1-propanol can be formed in this way at the low temperature of 10 K. Propanal has already been detected in space. 1-propanol is an astrobiologically relevant molecule, as it is a primary alcohol, and has not been astronomically detected. Propanal is the major product formed in the C2H2 + CO + H experiment, and 1-propanol is detected in the subsequent propanal + H experiment. The results are published in Qasim et al. (2019c). ALMA observations towards IRAS 16293-2422B are discussed and provide a 1-propanol:propanal upper limit of < 0.35 - 0.55, which are complemented by computationally-derived activation barriers in addition to the performed laboratory experiments.

astro-ph.SR↗

arXiv2019

Formation of interstellar propanal and 1-propanol ice: a pathway involving solid-state CO hydrogenation

1-propanol (CH3CH2CH2OH) is a three carbon-bearing representative of primary linear alcohols that may have its origin in the cold dark cores in interstellar space. To test this, we investigated in the laboratory whether 1-propanol ice can be formed along pathways possibly relevant to the prestellar core phase. We aim to show in a two-step approach that 1-propanol can be formed through reaction steps that are expected to take place during the heavy CO freeze-out stage by adding C2H2 into the CO + H hydrogenation network via the formation of propanal (CH3CH2CHO) as an intermediate and its subsequent hydrogenation. Temperature programmed desorption-quadrupole mass spectrometry (TPD-QMS) is used to identify the newly formed propanal and 1-propanol. Reflection absorption infrared spectroscopy (RAIRS) is used as a complementary diagnostic tool. The mechanisms that can contribute to the formation of solid-state propanal and 1-propanol, as well as other organic compounds, during the heavy CO freeze-out stage are constrained by both laboratory experiments and theoretical calculations. Here it is shown that recombination of HCO radicals, formed upon CO hydrogenation, with radicals formed upon C2H2 processing - H2CCH and H3CCH2 - offers possible reaction pathways to solid-state propanal and 1-propanol formation. This extends the already important role of the CO hydrogenation chain in the formation of larger COMs (complex organic molecules). The results are used to compare with ALMA observations. The resulting 1-propanol:propanal ratio concludes an upper limit of < 0:35-0:55, which is complemented by computationally-derived activation barriers in addition to the experimental results.

astro-ph.SR↗

arXiv2019

Extension of the HCOOH and CO2 solid-state reaction network during the CO freeze-out stage: inclusion of H2CO

Formic acid (HCOOH) and carbon dioxide (CO2) are simple species that have been detected in the interstellar medium. The solid-state formation pathways of these species under experimental conditions relevant to prestellar cores are primarily based off of weak infrared transitions of the HOCO complex and usually pertain to the H2O-rich ice phase, and therefore more experimental data are desired. In this article, we present a new and additional solid-state reaction pathway that can form HCOOH and CO2 ice at 10 K 'non-energetically' in the laboratory under conditions related to the "heavy" CO freeze-out stage in dense interstellar clouds, i.e., by the hydrogenation of an H2CO:O2 ice mixture. This pathway is used to piece together the HCOOH and CO2 formation routes when H2CO or CO reacts with H and OH radicals. Temperature programmed desorption - quadrupole mass spectrometry (TPD-QMS) is used to confirm the formation and pathways of newly synthesized ice species as well as to provide information on relative molecular abundances. Reflection absorption infrared spectroscopy (RAIRS) is additionally employed to characterize reaction products and determine relative molecular abundances. We find that for the conditions investigated in conjunction with theoretical results from the literature, H+HOCO and HCO+OH lead to the formation of HCOOH ice in our experiments. Which reaction is more dominant can be determined if the H+HOCO branching ratio is more constrained by computational simulations, as the HCOOH:CO2 abundance ratio is experimentally measured to be around 1.8:1. H+HOCO is more likely than OH+CO (without HOCO formation) to form CO2. Isotope experiments presented here further validate that H+HOCO is the dominant route for HCOOH ice formation in a CO-rich CO:O2 ice mixture that is hydrogenated. These data will help in the search and positive identification of HCOOH ice in prestellar cores.

astro-ph.SR↗

arXiv2019

Alcohols on the rocks: solid-state formation in a H3CCCH + OH cocktail under dark cloud conditions

A number of recent experimental studies have shown that solid-state complex organic molecules (COMs) can form under conditions that are relevant to the CO freeze-out stage in dense clouds. In this work, we show that alcohols can be formed well before the CO freeze-out stage (i.e., in the H2O-rich ice phase). This joint experimental and computational investigation shows that the isomers, n- and i-propanol (H3CCH2CH2OH and H3CCHOHCH3) and n- and i-propenol (H3CCHCHOH and H3CCOHCH2), can be formed in radical-addition reactions starting from propyne (H3CCCH) + OH at the low temperature of 10 K, where H3CCCH is one of the simplest representatives of stable carbon chains already identified in the interstellar medium (ISM). The resulting average abundance ratio of 1:1 for n-propanol:i-propanol is aligned with the conclusions from the computational work that the geometric orientation of strongly interacting species is influential to the extent of which 'mechanism' is participating, and that an assortment of geometries leads to an averaged-out effect. Three isomers of propanediol are also tentatively identified in the experiments. It is also shown that propene and propane (H3CCHCH2 and H3CCH2CH3) are formed from the hydrogenation of H3CCCH. Computationally-derived activation barriers give additional insight into what types of reactions and mechanisms are more likely to occur in the laboratory and in the ISM. Our findings not only suggest that the alcohols studied here share common chemical pathways and therefore can show up simultaneously in astronomical surveys, but also that their extended counterparts that derive from polyynes containing H3C(CC)nH structures may exist in the ISM. Such larger species, like fatty alcohols, are the possible constituents of simple lipids that primitive cell membranes on the early Earth are thought to be partially composed of.

astro-ph.GA↗