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Harold Linnartz

Publications and source records attributed to Harold Linnartz.

At least 37 records · Page 2Linked to original sources

Carbon Atom Reactivity with Amorphous Solid Water: H$_2$O Catalyzed Formation of H$_2$CO

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.

astro-ph.GA↗

Methane formation in cold regions from carbon atoms and molecular hydrogen

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.

astro-ph.GA↗

Infrared spectra of complex organic molecules in astronomically relevant ice matrices. III. Methyl formate and its tentative solid-state detection

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 $μ$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.

astro-ph.SR↗

Structural investigation of doubly-dehydrogenated pyrene cations

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.

astro-ph.GA↗

Exocomets from a Solar System Perspective

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.

astro-ph.EP↗

Searches for Interstellar HCCSH and H$_2$CCS

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.

astro-ph.GA↗

The Need for Laboratory Measurements and Ab Initio Studies to Aid Understanding of Exoplanetary Atmospheres

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.

astro-ph.EP↗

Cavity Ring-down UV spectroscopy of the C$^2Σ^+$-X$^2Π$ electronic transition of CH

Rotationally resolved spectra of the C$^2Σ^+$-X$^2Π$ 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) Å for the C$^2Σ^+$ 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.

physics.chem-ph↗

Laboratory photo-chemistry of covalently bonded fluorene clusters: observation of an interesting PAH bowl-forming mechanism

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.

astro-ph.IM↗

The EDIBLES survey IV. Cosmic ray ionization rates in diffuse clouds from near-ultraviolet observations of interstellar OH$^+$

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) $A^3Π-X^3Σ^-$ 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 $ζ_p$ in the targeted diffuse interstellar clouds. For the ten selected targets, we obtain a range of values for $ζ_p$ 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.

astro-ph.GA↗

From planes to bowls: photodissociation of the bisanthenequinone cation

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.

physics.atm-clus↗

Infrared Spectra of Hexa-peri-hexabenzocoronene Cations:HBC+ and HBC2+

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 $μ$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$^{-1}$($μ$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$^{-1}$($μ$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 $μ$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 $μ$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 $μ$m range as a diagnostic tool for the edge topology of large PAHs in space.

astro-ph.IM↗

Laboratory gas-phase infrared spectra of two astronomically relevant PAH cations: diindenoperylene, C$_{32}$H$_{16}$$^+$ and dicoronylene, C$_{48}$H$_{20}$$^+$

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 $μ$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$^{-1}$($μ$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$^{-1}$($μ$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 $μ$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.

astro-ph.IM↗

First Results of an ALMA Band 10 Spectral Line Survey of NGC 6334I: Detections of Glycolaldehyde (HC(O)CH$_2$OH) and a New Compact Bipolar Outflow in HDO and CS

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.

astro-ph.GA↗

The ESO Diffuse Interstellar Bands Large Exploration Survey: EDIBLES I. Project description, survey sample and quality assessment

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.

astro-ph.GA↗

C$_{60}^+$ and the Diffuse Interstellar Bands: An Independent Laboratory Check

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 Å. In the following year additional laboratory spectra were linked to three other and weaker DIBs at 9428, 9366, and 9349 Å. 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) Å, 9576.7(1) Å, 9427.5(1) Å, and 9364.9(1) Å. The corresponding band widths have been derived and the relative band intensity ratios are discussed.

astro-ph.GA↗

Formation of Glycerol through Hydrogenation of CO ice under Prestellar Core Conditions

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.

astro-ph.SR↗

Efficient Surface Formation Route of Interstellar Hydroxylamine through NO Hydrogenation II: the multilayer regime in interstellar relevant ices

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.

astro-ph.GA↗