Tag Archives: Chemical Physics

Identification of interstellar cyanamide towards the hot molecular core G358.93-0.03 MM1 [GA]

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http://arxiv.org/abs/2305.05578


The amide-related molecules are essential for the formation of the other complex bio-molecules and an understanding of the prebiotic chemistry in the interstellar medium (ISM). We presented the first detection of the rotational emission lines of the amide-like molecule cyanamide (NH${2}$CN) towards the hot molecular core G358.93$-$0.03 MM1 using the Atacama Large Millimeter/Submillimeter Array (ALMA). Using the rotational diagram model, the derived column density of NH${2}$CN towards the G358.93$-$0.03 MM1 was (5.9$\pm$2.5)$\times$10$^{14}$ cm$^{-2}$ with a rotational temperature of 100.6$\pm$30.4 K. The derived fractional abundance of NH${2}$CN towards the G358.93$-$0.03 MM1 with respect to H${2}$ was (4.72$\pm$2.0)$\times$10$^{-10}$, which is very similar to the existent three-phase warm-up chemical model abundances of NH${2}$CN. We compare the estimated abundance of NH${2}$CN towards G358.93$-$0.03 MM1 with other sources, and we observe the abundance of NH${2}$CN towards G358.93$-$0.03 MM1 is nearly similar to that of the sculptor galaxy NGC 253 and the low-mass protostars IRAS 16293-2422 B and NGC 1333 IRAS4A2. We also discussed the possible formation mechanisms of NH${2}$CN towards the hot molecular cores and hot corinos, and we find that the NH${2}$CN molecule was created in the grain-surfaces of G358.93-0.03 MM1 via the neutral-neutral reaction between NH${2}$ and CN.

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A. Mannna and S. Pal
Wed, 10 May 23
40/65

Comments: Published in Astrophysics and Space Science

Low-Temperature Kinetics for the N + NO reaction: Experiment Guides the Way [GA]

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http://arxiv.org/abs/2305.05305


The reaction N(4S) + NO -> O(3P) + N2 plays a pivotal role in the conversion of atomic to molecular nitrogen in dense interstellar clouds and in the atmosphere. Here we report a joint experimental and computational investigation of the N + NO reaction with the aim of providing improved constraints on its low temperature reactivity. Thermal rates were measured over the 50 to 296 K range in a continuous supersonic flow reactor coupled with pulsed laser photolysis and laser induced fluorescence for the production and detection of N(4S) atoms, respectively. With decreasing temperature, the experimentally measured reaction rate was found to monotonously increase up to a value of (6.6 +- 1.3) x 10-11 cm3 s-1 at 50 K. To confirm this finding, quasi-classical trajectory simulations were carried out on a previously validated, full-dimensional potential energy surface (PES). However, around 50 K the computed rates decreased which required re-evaluation of the reactive PES in the long-range part due to a small spurious barrier with height 40 K in the entrance channel. By exploring different correction schemes the measured thermal rates can be adequately reproduced, displaying a clear negative temperature dependence over the entire temperature range. The possible astrochemical implications of an increased reaction rate at low temperature are also discussed.

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K. Hickson, J. Veliz, D. Koner, et. al.
Wed, 10 May 23
45/65

Comments: 28 pages, 6 figures and 2 tables in the main article. 3 figures and 1 table in the supplementary information. Accepted for publication in PCCP

Applications of Gaussian Processes at Extreme Lengthscales: From Molecules to Black Holes [CL]

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http://arxiv.org/abs/2303.14291


In many areas of the observational and experimental sciences data is scarce. Data observation in high-energy astrophysics is disrupted by celestial occlusions and limited telescope time while data derived from laboratory experiments in synthetic chemistry and materials science is time and cost-intensive to collect. On the other hand, knowledge about the data-generation mechanism is often available in the sciences, such as the measurement error of a piece of laboratory apparatus. Both characteristics, small data and knowledge of the underlying physics, make Gaussian processes (GPs) ideal candidates for fitting such datasets. GPs can make predictions with consideration of uncertainty, for example in the virtual screening of molecules and materials, and can also make inferences about incomplete data such as the latent emission signature from a black hole accretion disc. Furthermore, GPs are currently the workhorse model for Bayesian optimisation, a methodology foreseen to be a guide for laboratory experiments in scientific discovery campaigns. The first contribution of this thesis is to use GP modelling to reason about the latent emission signature from the Seyfert galaxy Markarian 335, and by extension, to reason about the applicability of various theoretical models of black hole accretion discs. The second contribution is to extend the GP framework to molecular and chemical reaction representations and to provide an open-source software library to enable the framework to be used by scientists. The third contribution is to leverage GPs to discover novel and performant photoswitch molecules. The fourth contribution is to introduce a Bayesian optimisation scheme capable of modelling aleatoric uncertainty to facilitate the identification of material compositions that possess intrinsic robustness to large scale fabrication processes.

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R. Griffiths
Tue, 28 Mar 23
25/81

Comments: PhD Thesis submitted at the University of Cambridge, August 2022. The thesis is based on a number of previous works also available on arXiv (see Introduction)

A sequential acid-base (SAB) mechanism in the interstellar medium: The emergence of cis formic acid in dark molecular clouds [GA]

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http://arxiv.org/abs/2301.07450


The abundance ratios between isomers of a COM observed in the ISM provides valuable information about the chemistry and physics of the gas and eventually, the history of molecular clouds. In this context, the origin of an abundance of c-HCOOH acid of only 6% the isomer c-HCOOH abundance in cold cores, remains unknown. Herein, we explain the presence of c-HCOOH in dark molecular clouds through the destruction and back formation of c-HCOOH and t-HCOOH in a cyclic process that involves HCOOH and highly abundant molecules such as HCO+ and NH3. We use high-level ab initio methods to compute the potential energy profiles for the cyclic destruction/formation routes of c-HCOOH and t-HCOOH. Global rate constants and branching ratios were calculated based on the transition state theory and the master equation formalism under the typical conditions of the ISM. The destruction of HCOOH by reaction with HCO+ in the gas phase leads to three isomers of the cation HC(OH)2+. The most abundant cation can react in a second step with other abundant molecules of the ISM like NH3 to form back c-HCOOH and t-HCOOH. This mechanism explains the formation of c-HCOOH in dark molecular clouds. Considering this mechanism, the fraction of c-HCOOH with respect t-HCOOH is 25.7%. To explain the 6% reported by the observations we propose that further destruction mechanisms of the cations of HCOOH should be taken into account. The sequential acid-base (SAB) mechanism proposed in this work involves fast processes with very abundant molecules in the ISM. Thus, HCOOH very likely suffers our proposed transformations in the conditions of dark molecular clouds. This is a new approach in the framework of the isomerism of organic molecules in the ISM which has the potential to try to explain the ratio between isomers of organic molecules detected in the ISM.

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J. Concepción, I. Jiménez-Serra, J. Corchado, et. al.
Thu, 19 Jan 23
32/100

Comments: N/A

Glycine amino acid transformation under impacts by small solar system bodies, simulated via high-pressure torsion method [EPA]

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http://arxiv.org/abs/2301.06927


Impacts by small solar system bodies (meteoroids, asteroids, comets and transitional objects) are characterized by a combination of energy dynamics and chemical modification on both terrestrial and small solar system bodies. In this context, the discovery of glycine amino acid in meteorites and comets has led to a hypothesis that impacts by astronomical bodies could contribute to delivery and polymerization of amino acids in the early Earth to generate proteins as essential molecules for life. Besides the possibility of abiotic polymerization of glycine, its decomposition by impacts could generate reactive groups to form other essential organic biomolecules. In this study, the high-pressure torsion (HPT) method, as a new platform for simulation of impacts by small solar system bodies, was applied to glycine. In comparison with high-pressure shock experiments, the HPT method simultaneously introduces high pressure and deformation strain. It was found that glycine was not polymerized in the experimental condition assayed, but partially decomposed to ethanol under pressures of 1 and 6 GPa and shear strains of <120 m/m. The detection of ethanol implies the inherent availability of remaining nitrogen-containing groups, which can incorporate to the formation of other organic molecules at the impact site. In addition, this finding highlights a possibility of the origin of ethanol previously detected in comets.

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K. Edalati, I. Taniguchi, R. Floriano, et. al.
Wed, 18 Jan 23
58/133

Comments: N/A

A DZ white dwarf with a 30 MG magnetic field [SSA]

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http://arxiv.org/abs/2301.04665


Magnetic white dwarfs with field strengths below 10 MG are easy to recognise since the Zeeman splitting of spectral lines appears proportional to the magnetic field strength. For fields $\geq 100$ MG, however, transition wavelengths become chaotic, requiring quantum-chemical predictions of wavelengths and oscillator strengths with a non-perturbative treatment of the magnetic field. While highly accurate calculations have previously been performed for hydrogen and helium, the variational techniques employed become computationally intractable for systems with more than three to four electrons. Modern computational techniques, such as finite-field coupled-cluster theory, allow the calculation of many-electron systems in arbitrarily strong magnetic fields. Because around 25 percent of white dwarfs have metal lines in their spectra, and some of those are also magnetic, the possibility arises for some metals to be observed in very strong magnetic fields, resulting in unrecognisable spectra. We have identified SDSSJ114333.48+661531.83 as a magnetic DZ white dwarf, with a spectrum exhibiting many unusually shaped lines at unknown wavelengths. Using atomic data calculated from computational finite-field coupled-cluster methods, we have identified some of these lines arising from Na, Mg, and Ca. Surprisingly, we find a relatively low field strength of 30 MG, where the large number of overlapping lines from different elements make the spectrum challenging to interpret at a much lower field strength than for DAs and DBs. Finally we model the field structure of SDSSJ1143+6615 finding the data are consistent with an offset dipole.

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M. Hollands, S. Stopkowicz, M. Kitsaras, et. al.
Fri, 13 Jan 23
13/72

Comments: 17 pages, 8 figures, Accepted for publication in MNRAS

Investigating the impact of reactions of C and CH with molecular hydrogen on a glycine gas-grain network [GA]

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http://arxiv.org/abs/2301.04324


The impact of including the reactions of C and CH with molecular hydrogen in a gas-grain network is assessed via a sensitivity analysis. To this end, we vary 3 parameters, namely, the efficiency for the reaction \ce{C + H2 -> CH2}, and the cosmic ray ionisation rate, with the third parameter being the final density of the collapsing dark cloud. A grid of 12 models is run to investigate the effect of all parameters on the final molecular abundances of the chemical network. We find that including reactions with molecular hydrogen alters the hydrogen economy of the network; since some species are hydrogenated by molecular hydrogen, atomic hydrogen is freed up. The abundances of simple molecules produced from hydrogenation, such as \ce{CH4}, \ce{CH3OH} and \ce{NH3}, increase, and at the same time, more complex species such as glycine and its precursors see a significant decrease in their final abundances. We find that the precursors of glycine are being preferentially hydrogenated, and therefore glycine itself is produced less efficiently.

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J. Heyl, T. Lamberts, S. Viti, et. al.
Thu, 12 Jan 23
43/68

Comments: 11 pages, 3 figures, accepted for publication in MNRAS

Where does the energy go during the interstellar NH$_3$ formation on water ice? A computational study [GA]

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http://arxiv.org/abs/2212.14271


In the coldest (10–20 K) regions of the interstellar medium, the icy surfaces of interstellar grains serve as solid-state supports for chemical reactions. Among their plausible roles, that of third body is advocated, in which the reaction energies of surface reactions dissipate throughout the grain, stabilizing the product. This energy dissipation process is poorly understood at the atomic scale, although it can have a high impact on Astrochemistry. Here, we study, by means of quantum mechanical simulations, the formation of NH3 via successive H-additions to atomic N on water ice surfaces, paying special attention to the third body role. We first characterize the hydrogenation reactions and the possible competitive processes (i.e., H-abstractions), in which the H-additions are more favourable than the H-abstractions. Subsequently, we study the fate of the hydrogenation reaction energies by means of ab initio molecular dynamics simulations. Results show that around 58–90\% of the released energy is quickly absorbed by the ice surface, inducing a temporary increase of the ice temperature. Different energy dissipation mechanisms are distinguished. One mechanism, more general, is based on the coupling of the highly excited vibrational modes of the newly formed species and the libration modes of the icy water molecules. A second mechanism, exclusive during the NH$_3$ formation, is based on the formation of a transient H$_3$O$^+$/NH$_2^-$ ion pair, which significantly accelerates the energy transfer to the surface. Finally, the astrophysical implications of our findings relative to the interstellar synthesis of NH$_3$ and its chemical desorption into the gas are discussed.

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S. Ferrero, S. Pantaleone, C. Ceccarelli, et. al.
Mon, 2 Jan 23
36/44

Comments: N/A

Long-Range Complex in the HC3N + CN Potential Energy Surface: Ab Initio Calculations and Intermolecular Potential [GA]

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http://arxiv.org/abs/2212.11312


In this work we characterize an initial van der Waals adduct in the potential energy surface of reaction between cyanoacetylene HC3N and the cyano radical. The geometry of the CN-HC3N adduct has been optimized through calculations employing ab initio methods. Results show that the energy of the adduct lays below the reactants. Additionally, a saddle point that connects the adduct to an important intermediate of the PES has been localized, with energy below the reactants. Calculations of the intermolecular potential have been performed and results show that the energy of the van der Waals adduct is higher than estimated with the ab initio methods.

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E. Aragão, L. Mancini, N. Faginas-Lago, et. al.
Fri, 23 Dec 22
52/58

Comments: 13 pages, 5 figures. Preprint version submitted to LNCS (Springer) ICCSA2021

The S$^+$($^4$S) + SiH$_{2}$($^1$A$_1$) Reaction: Toward the Synthesis of Interstellar SiS [CL]

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http://arxiv.org/abs/2212.11754


We have performed a theoretical investigation of the S$^+$($^4$S) + SiH${2}$($^1$A$_1$) reaction, a possible formation route of the HSiS$^+$ and SiSH$^+$ cations that are alleged to be precursors of interstellar silicon sulfide, SiS. Electronic structure calculations allowed us to identify the main reaction pathways for the systems. The reaction has two exothermic channels leading to the isomeric species $^3$HSiS$^{+}$ and $^3$SiSH$^{+}$ formed in conjunction with H atoms. The reaction is not characterized by an entrance barrier and, therefore, it is believed to be fast also under the very low temperature conditions of interstellar clouds. The two ions are formed in their first electronically excited state because of the spin multiplicity of the overall potential energy surface. In addition, following the suggestion that neutral species are formed by proton transfer of protonated cations to ammonia, we have derived the potential energy surface for the reactions $^3$HSiS$^{+}$/$^3$SiSH$^{+}$ + NH${3}$($^{1}$A$_1$).

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L. Mancini, M. Trinari, E. Aragão, et. al.
Fri, 23 Dec 22
56/58

Comments: 15 pages, 7 figures. Preprint version submitted to LNCS (Springer) ICCSA2022

A computational analysis of the reaction of atomic oxygen O(3P) with acrylonitrile [GA]

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http://arxiv.org/abs/2212.10396


The work is focused on the characterization of a long-range interacting complex in the reaction between atomic oxygen, in its ground state O(3P) and acrylonitrile CH2CHCN, also known as vinyl cyanide or cyano ethylene, through electronic structure calculations. Different ab initio methods have been used in order to understand which functional provides a better description of the long-range interaction. The results of the work suggest that B2PLYPD3 gives the best description of the long-range interaction, while CAM-B3LYP represents the best compromise between chemical accuracy and computational cost.

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L. Mancini and E. Aragão
Wed, 21 Dec 22
5/81

Comments: 13 pages, 4 figures. Preprint version submitted to LNCS (Springer) ICCSA2021

Dynamics of the Great Oxidation Event from a 3D photochemical-climate model [EPA]

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http://arxiv.org/abs/2212.01389


From the Archean toward the Proterozoic, the Earth’s atmosphere underwent a major shift from anoxic to oxic conditions, around 2.4 to 2.1 Gyr, known as the Great Oxidation Event (GOE). This rapid transition may be related to an atmospheric instability caused by the formation of the ozone layer. Previous works were all based on 1D photochemical models. Here, we revisit the GOE with a 3D photochemical-climate model to investigate the possible impact of the atmospheric circulation and the coupling between the climate and the dynamics of the oxidation. We show that the diurnal, seasonal and transport variations do not bring significant changes compared to 1D models. Nevertheless, we highlight a temperature dependence for atmospheric photochemical losses. A cooling during the late Archean could then have favored the triggering of the oxygenation. In addition, we show that the Huronian glaciations, which took place during the GOE, could have introduced a fluctuation in the evolution of the oxygen level. Finally, we show that the oxygen overshoot which is expected to have occurred just after the GOE, was likely accompanied by a methane overshoot. Such high methane concentrations could have had climatic consequences and could have played a role in the dynamics of the Huronian glaciations.

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A. Jaziri, B. Charnay, F. Selsis, et. al.
Tue, 6 Dec 22
27/87

Comments: N/A

A quantum-mechanical investigation of O($^3P$) + CO scattering cross sections at superthermal collision energies [CL]

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http://arxiv.org/abs/2212.01799


The kinetics and energetic relaxation associated with collisions between fast and thermal atoms are of fundamental interest for escape and therefore also for the evolution of the Mars atmosphere. The total and differential cross-sections of fast O($^3P$) atom collisions with CO have been calculated from quantum mechanical calculations. The cross-sections are computed at collision energies from 0.4 to 5 eV in the center-of-mass frame relevant to the planetary science and astrophysics. All the three potential energy surfaces ($^3$A’, $^3$A” and 2 $^3$A” symmetry) of O($^3P$) + CO collisions separating to the atomic ground state have been included in calculations of cross-sections. The cross-sections are computed for all three isotopes of energetic O($^3P$) atoms collisions with CO. The isotope dependence of the cross-sections are compared. Our newly calculated data on the energy relaxation of O atoms and their isotopes with CO molecules will be very useful to improve the modeling of escape and energy transfer processes in the Mars’ upper atmosphere.

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S. Chhabra, M. Gacesa, M. Khalil, et. al.
Tue, 6 Dec 22
62/87

Comments: 8 pages, 6 figures

Energy transfer and restructuring in amorphous solid water upon consecutive irradiation [GA]

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http://arxiv.org/abs/2211.16217


Interstellar and cometary ices play an important role in the formation of planetary systems around young stars. Their main constituent is amorphous solid water (ASW). Although ASW is widely studied, vibrational energy dissipation and structural changes due to vibrational excitation are less well understood. The hydrogen-bonding network is likely a crucial component in this. Here we present experimental results on hydrogen-bonding changes in ASW induced by the intense, nearly monochromatic mid-IR free-electron laser (FEL) radiation of the FELIX-2 beamline at the HFML-FELIX facility at the Radboud University in Nijmegen, the Netherlands. Structural changes in ASW are monitored by reflection-absorption infrared spectroscopy and depend on the irradiation history of the ice. The experiments show that FEL irradiation can induce changes in the local neighborhood of the excited molecules due to energy transfer. Molecular Dynamics simulations confirm this picture: vibrationally excited molecules can reorient for a more optimal tetrahedral surrounding without breaking existing hydrogen bonds. The vibrational energy can transfer through the hydrogen-bonding network to water molecules that have the same vibrational frequency. We hence expect a reduced energy dissipation in amorphous material with respect to crystalline material due to the inhomogeneity in vibrational frequencies as well as the presence of specific hydrogen-bonding defect sites which can also hamper the energy transfer.

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H. Cuppen, J. Noble, S. Coussan, et. al.
Wed, 30 Nov 22
34/81

Comments: 34 page, 9 figures

Study of vibrational spectra of polycyclic aromatic hydrocarbons with phenyl side group [GA]

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http://arxiv.org/abs/2211.13684


Computational study of polycyclic aromatic hydrocarbons (PAHs) with phenyl side group substituted at different positions is reported. The infrared spectral variations due to the position of phenyl substitution, ionization state and the size of the molecules are discussed and possible contribution of phenyl-PAHs to the mid-infrared emission features from astrophysical objects is analyzed. Structurally phenyl group substitution at 2nd position gives more stable species compared to substitution at other positions. Phenyl-PAHs exhibit new aromatic bands near 695 and 741 cm$^{-1}$ (14.4 and 13.5 $\mu$m), due to contribution from quintet C-H wag, that compare well with minor features at 14.2 and 13.5 $\mu$m observed in several astrophysical objects. Just as in plain PAHs, the C-C stretch vibrational modes ($\sim$1600 cm$^{-1}$) have negligible intensity in neutrals, but the cations of all phenyl-PAHs exhibit significantly strong phenyl group C-C stretch peak close to class B type 6.2 $\mu$m astrophysical band. In 2-phenylpyrene, it is the neutral molecule that exhibits this strong feature in the 6.2 $\mu$m range along with other features that match with sub-features at 6.66 and 6.9 $\mu$m, observed in astronomical spectra of some late type objects. The substitution of phenyl side group at solo position shifts the C-C stretch mode of parent PAH close to the region of 6.2 $\mu$m astrophysical band. The results indicate possibility of phenyl-PAHs in space and the bottom-up formation of medium sized compact PAHs with phenyl side group in carbon rich cool circumstellar shells. Phenyl-PAHs need to be considered in modelling mid-infrared emission spectra of various astrophysical objects.

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A. Maurya, R. Singh and S. Rastogi
Mon, 28 Nov 22
69/93

Comments: 45 papges including 15 Figures and 3 Tables

The CO$_2$ Profile and Analytical Model for the Pioneer Venus Large Probe Neutral Mass Spectrometer [EPA]

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http://arxiv.org/abs/2211.12557


We present a significantly updated CO$_2$ altitude profile for Venus (64.2-0.9 km) and provide support for a potential deep lower atmospheric haze of particles (17 km and lower). We extracted this information by developing a new analytical model for mass spectra obtained by the Pioneer Venus Large Probe (PVLP) Neutral Mass Spectrometer (LNMS). Our model accounts for changes in LNMS configuration and output during descent and enables the disentanglement of isobaric species via a data fitting routine that adjusts for mass-dependent changes in peak shape. The model yields CO$_2$ in units of density (kg m-3), isotope ratios for $^{13}$C/$^{12}$C and $^{18}$O/$^{16}$O, and 14 measures of CO$_2$ density across 55.4-0.9 km, which represents the most complete altitude profile for CO$_2$ at 60 km towards the surface to date. The CO$_2$ density profile is also consistent with the pressure, temperature, and volumetric gas measurements from the PVLP and VeNeRa spacecraft. Nominal and low-noise operations for the LNMS mass analyzer are supported by the behaviors (e.g., ionization yields, fragmentation yields, and peak shapes) of several internal standards (e.g., CH$^{3+}$, CH$^{4+}$, $^{40}$Ar$^+$, $^{136}$Xe$^{2+}$, and $^{136}$Xe$^+$), which were tracked across the descent. Lastly, our review of the CO$_2$ profile and LNMS spectra reveals hitherto unreported partial and rapidly clearing clogs of the inlet in the lower atmosphere, along with several ensuing data spikes at multiple masses. Together, these observations suggest that atmospheric intake was impacted by particles at 17 km (and lower) and that rapid particle degradation at the inlet yielded a temporary influx of mass signals into the LNMS.

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R. Mogul, S. Limaye and M. Way
Thu, 24 Nov 22
12/71

Comments: Accepted, Nov. 2022

The CO2 Profile and Analytical Model for the Pioneer Venus Large Probe Neutral Mass Spectrometer [EPA]

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http://arxiv.org/abs/2211.12557


We present a significantly updated CO2 altitude profile for Venus (64.2-0.9 km) and provide support for a potential deep lower atmospheric haze of particles (17 km and lower). We extracted this information by developing a new analytical model for mass spectra obtained by the Pioneer Venus Large Probe (PVLP) Neutral Mass Spectrometer (LNMS). Our model accounts for changes in LNMS configuration and output during descent and enables the disentanglement of isobaric species via a data fitting routine that adjusts for mass-dependent changes in peak shape. The model yields CO2 in units of density (kg m-3), isotope ratios for 13C/12C and 18O/16O, and 14 measures of CO2 density across 55.4-0.9 km, which represents the most complete altitude profile for CO2 at 60 km towards the surface to date. The CO2 density profile is also consistent with the pressure, temperature, and volumetric gas measurements from the PVLP and VeNeRa spacecraft. Nominal and low-noise operations for the LNMS mass analyzer are supported by the behaviors (e.g., ionization yields, fragmentation yields, and peak shapes) of several internal standards (e.g., CH3+, CH4+, 40Ar+, 136Xe2+, and 136Xe+), which were tracked across the descent. Lastly, our review of the CO2 profile and LNMS spectra reveals hitherto unreported partial and rapidly clearing clogs of the inlet in the lower atmosphere, along with several ensuing data spikes at multiple masses. Together, these observations suggest that atmospheric intake was impacted by particles at 17 km (and lower) and that rapid particle degradation at the inlet yielded a temporary influx of mass signals into the LNMS.

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R. Mogul, S. Limaye and M. Way
Thu, 24 Nov 22
34/71

Comments: Accepted, Nov. 2022

Quantum chemical computations of gas-phase glycolaldehyde deuteration and constraints to its formation route [CL]

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http://arxiv.org/abs/2211.11563


Despite the detection of numerous interstellar complex organic molecules (iCOMs) for decades, it is still a matter of debate whether they are synthesized in the gas-phase or on the icy surface of interstellar grains. In the past, molecular deuteration has been used to constrain the formation paths of small and abundant hydrogenated interstellar species. More recently, the deuteration degree of formamide, one of the most interesting iCOM, has also been explained in the hypothesis that it is formed by the gas-phase reaction NH$_2$ + H$_2$CO. In this article, we aim at using molecular deuteration to constrain the formation of another iCOM, glycolaldehyde, which is an important prebiotic species. More specifically, we have performed dedicated electronic structure and kinetic calculations to establish the glycolaldehyde deuteration degree in relation to that of ethanol, which is its possible parent species according to the suggestion of Skouteris et al. (2018). We found that the abundance ratio of the species containing one D-atom over the all-protium counterpart depends on the produced D isotopomer and varies from 0.9 to 0.5. These theoretical predictions compare extremely well with the monodeuterated isotopomers of glycolaldehyde and that of ethanol measured towards the Solar-like protostar IRAS 16293-2422, supporting the hypothesis that glycolaldehyde could be produced in the gas-phase for this source. In addition, the present work confirms that the deuterium fractionation of iCOMs cannot be simply anticipated based on the deuterium fractionation of the parent species but necessitates a specific study, as already shown for the case of formamide.

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F. Vazart, C. Ceccarelli, D. Skouteris, et. al.
Tue, 22 Nov 22
49/83

Comments: Accepted by ApJ

Experimental Characterization of the Energetics of Low-temperature Surface Reactions [CL]

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http://arxiv.org/abs/2211.04437


Astrochemical surface reactions are thought to be responsible for the formation of complex organic molecules, which are of potential importance for the origin of life. In a situation, when the chemical composition of dust surfaces is not precisely known, the fundamental knowledge concerning such reactions gains significance. We describe an experimental technique, which can be used to measure the energy released in reactions of a single pair of reactants. These data can be directly compared with the results of quantum chemical computations leading to unequivocal conclusions regarding the reaction pathways and the presence of energy barriers. It allows for predicting the outcomes of astrochemical surface reactions with higher accuracy compared to that achieved based on gas-phase studies. However, for the highest accuracy, some understanding of the catalytic influence of specific surfaces on the reactions is required. The new method was applied to study the reactions of C atoms with H2, O2, and C2H2. The formation of HCH, CO + O, and triplet cyclic-C3H2 products has been revealed, correspondingly.

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T. Henning and S. Krasnokutski
Wed, 9 Nov 22
9/76

Comments: N/A

An accurate set of H$_3$O$^+ -$ H$_2$ collisional rate coefficients for non-LTE modelling of warm interstellar clouds [GA]

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http://arxiv.org/abs/2211.02309


Hydronium (H$_3$O$^+$) was first detected in 1986 in interstellar molecular clouds. It was reported in many galactic diffuse and dense regions, as well as in extragalactic sources. H$_3$O$^+$ plays a major role both in interstellar oxygen and water chemistry. However, despite the large number of H$_3$O$^+$ observations, its collisional excitation was investigated only partially. In the present work we study the state-to-state rotational de-excitation of $ortho$- and $para$-H$_3$O$^+$ in collisions both with $ortho$- and $para$-H$_2$. The cross sections are calculated within the close-coupling formalism using a highly accurate potential energy surface developed for this system. The rate coefficients are computed up to $300$ K kinetic temperature. Transitions between the lowest 21 rotation-inversion states were studied for $para$-H$_3$O$^+$, and the lowest 11 states for $ortho$-H$_3$O$^+$, i.e. all levels with rotational energies below 430 K ($\sim 300$ cm$^{-1}$) are considered (up to $j\leq5$). In order to estimate the impact of the new rate coefficients on the astrophysical models for H$_3$O$^+$, radiative transfer calculations were also carried out. We have examined how the new collisional data affect the line intensities with respect to older data previously used for the interpretation of observations. By analysing all detected transitions we find that our new, accurate rate coefficients have a significant impact (typically within a factor of 2) on radiation temperatures, allowing more accurate estimation of column densities and relative abundances of hydronium, especially in warm molecular clouds, paving the path towards better interpretation of interstellar water and oxygen chemistry.

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S. Demes, F. Lique, A. Faure, et. al.
Mon, 7 Nov 22
43/67

Comments: 13 pages, 7 figures

Detection of complex nitrogen-bearing molecule ethyl cyanide towards the hot molecular core G10.47+0.03 [GA]

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http://arxiv.org/abs/2211.01608


The studies of the complex molecular lines towards the hot molecular cores at millimeter and submillimeter wavelengths provide instructive knowledge about the chemical complexity in the interstellar medium (ISM). We presented the detection of the rotational emission lines of the complex nitrogen-bearing molecule ethyl cyanide (C${2}$H${5}$CN) towards the hot molecular core G10.47+0.03 using the Atacama Large Millimeter/Submillimeter Array (ALMA) band 4 observations. The estimated column density of C${2}$H${5}$CN towards G10.47+0.03 was (9.5$\pm$0.1)$\times$10$^{16}$ cm$^{-2}$ with the rotational temperature of 223.8$\pm$4.3 K. The estimated fractional abundance of C${2}$H${5}$CN with respect to H${2}$ towards G10.47+0.03 was 1.90$\times$10$^{-8}$. We observed that the estimated fractional abundance of C${2}$H${5}$CN is nearly similar to the simulated abundance of C${2}$H${5}$CN which was predicted by the three-phase warm-up model from Garrod (2013). We also discuss the possible formation mechanism of C${2}$H${5}$CN towards the hot molecular cores and we claimed the barrierless and exothermic radical-radical reaction between CH${2}$ and CH${2}$CN is responsible for the production of high abundant C${2}$H$_{5}$CN ($\sim$10$^{-8}$) towards G10.47+0.03 during the warm-up phases.

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A. Manna and S. Pal
Fri, 4 Nov 22
51/84

Comments: 19 pages, 4 figures

Laboratory and astronomical discovery of magnesium dicarbide, MgC$_2$ [SSA]

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http://arxiv.org/abs/2210.17348


We report the detection of magnesium dicarbide, MgC$_2$, in the laboratory at centimeter wavelengths and assign $^{24}$MgC$_2$, $^{25}$MgC$_2$, and $^{26}$MgC$_2$ to 14 unidentified lines in the radio spectrum of the circumstellar envelope of the evolved carbon star IRC+10216. The structure of MgC$_2$ is found to be T-shaped with a highly ionic bond between the metal atom and the C$_2$ unit, analogous to other dicarbides containing electropositive elements. A two-temperature excitation model of the MgC$_2$ emission lines observed in IRC+10216 yields a very low rotational temperature of $6\pm1$ K, a kinetic temperature of $22\pm13$ K, and a column density of $(1.0 \pm 0.3) \times 10^{12}$ cm$^{-2}$. The abundance of MgC$_2$ relative to the magnesium-carbon chains MgCCH, MgC$_4$H, and MgC$_6$H is $1{:}2{:}22{:}20$ and provides a new constraint on the sequential radiative association-dissociative recombination mechanisms implicated in the production of metal-bearing molecules in circumstellar environments.

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P. Changala, H. Gupta, J. Cernicharo, et. al.
Tue, 1 Nov 22
92/100

Comments: 15 pages, 5 figures

ExoMol line lists — {XLVI}: Empirical rovibronic spectra of silicon mononitrate (SiN) covering the 6 lowest electronic states and 4 isotopologues [EPA]

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http://arxiv.org/abs/2210.12477


Silicon mononitride ($^{28}$Si$^{14}$N, $^{29}$Si$^{14}$N, $^{30}$Si$^{14}$N, $^{28}$Si$^{15}$N) line lists covering infrared, visible and ultraviolet regions are presented. The \name\ line lists produced by ExoMol include rovibronic transitions between six electronic states: \XS, \AS, \BS, \DS, \asi, \bsi. The \ai\ potential energy and coupling curves, computed at the multireference configuration interaction (MRCI/aug-cc-pVQZ) level of theory, are refined for the observed states by fitting their analytical representations to 1052 experimentally derived SiN energy levels determined from rovibronic bands belonging to the $X$–$X$, $A$–$X$ and $B$–$X$ electronic systems through the MARVEL procedure. The SiNful line lists are compared to previously observed spectra, recorded and calculated lifetimes, and previously calculated partition functions. SiNful is available via the \url{www.exomol.com} database.

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M. Semenov, N. Clark, S. Yurchenko, et. al.
Tue, 25 Oct 22
69/111

Comments: N/A

Molecular Structure, Dynamics, and Vibrational Spectroscopy of the Acetylene:Ammonia (1:1) Plastic Co-Crystal at Titan Conditions [CL]

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http://arxiv.org/abs/2210.12188


The Saturnian moon Titan has a thick, organic-rich atmosphere, and condensed phases of small organic molecules are anticipated to be stable on its surface. Of particular importance are crystalline phases of organics, known as cryominerals, which can play important roles in surface chemistry and geological processes on Titan. Many of these cryominerals could exhibit rich phase behavior, especially multicomponent cryominerals whose component molecules have multiple solid phases. One such cryomineral is the acetylene:ammonia (1:1) co-crystal, and here we use density functional theory-based ab initio molecular dynamics simulations to quantify its structure and dynamics at Titan conditions. We show that the acetylene:ammonia (1:1) co-crystal is a plastic co-crystal (or rotator phase) at Titan conditions because the ammonia molecules are orientationally disordered. Moreover, the ammonia molecules within this co-crystal rotate on picosecond timescales, and this rotation is accompanied by the breakage and reformation of hydrogen bonds between the ammonia hydrogens and the {\pi}-system of acetylene. The robustness of our predictions is supported by comparing the predictions of two density functional approximations at different levels of theory, as well as through the prediction of infrared and Raman spectra that agree well with experimental measurements. We anticipate that these results will aid in understanding geochemistry on the surface of Titan.

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A. Thakur and R. Remsing
Tue, 25 Oct 22
80/111

Comments: 11 pages, 9 figures, 2 tables

The effect of water and electron collisions in the rotational excitation of HF in comets [EPA]

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http://arxiv.org/abs/2210.11967


We present the first set of rate coefficients for the rotational excitation of the 7 lowest levels of hydrogen fluoride (HF) induced by collision with water molecules, the dominant collider in cometary comas, in the 5-150 K temperature range. The calculations are performed with a quantum statistical approach from an accurate rigid rotor ab initio interaction potential. Rate coefficients for excitation of HF by electron-impact are also computed, within the Born approximation, in the 10-10,000 K temperature range. These rate coefficients are then used in a simplified non-local thermodynamic equilibrium (non-LTE) model of a cometary coma that also includes solar radiative pumping and radiative decay. We investigate the range of H2O densities that lead to non-LTE populations of the rotational levels of HF. We show that to describe the excitation of HF in comets, considering collisions with both water molecules and electrons is needed as a result of the large dipole of HF.

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J. Loreau, A. Faure and F. Lique
Mon, 24 Oct 22
29/56

Comments: 8 pages

Computational Estimation of the Binding Energies of POx and HPOx (x=2,3) Species [SSA]

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http://arxiv.org/abs/2210.09359


The distribution of molecules between the gas and solid phase during star and planet formation, determines the trajectory of gas and grain surface chemistry, as well as the delivery of elements to nascent planets. This distribution is primarily set by the binding energies of different molecules to water ice surfaces. We computationally estimated the binding energies of ten astrochemically relevant P-bearing species on water surface, we also validate our method for 20 species with known binding energies. We used DFT calculations (M06-2X/aug-cc-pVDZ) to calculate the energetics of molecules and water-molecule clusters (1-3 H$_2$O molecules) and from this determined the binding energy by comparing the complex and the separate molecule and cluster energies. We also explore whether these estimates can be improved by first calibrating our computational method using experimentally measured binding energies. Using the 20 reference molecules we find that the 2H$_2$O cluster size yields the best binding energy estimates and that the application of a calibration to the data may improve the results for some classes of molecules, including more refractory species. Based on these calculations we find that, small P-bearing molecules such as PH$_3$, PN, PO, HPO, PO$_2$ and POOH are relatively volatile and should desorb prior or concomitantly with water ice, while H$_2$PO, HPO$_2$, PO$_3$, PO$_2$OH can strongly bind to any hydroxylated surface, and will likely remain on the interstellar grains surface past the desorbtion of water ice. The depletion of P-carriers on grains constitute a pathway for the inclusion of Phosphorous molecules in planets and planetesimals.

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E. Piacentino and K. Öberg
Wed, 19 Oct 22
60/87

Comments: N/A

An ab initio study of the rovibronic spectrum of sulphur monoxide (SO): diabatic vs. adiabatic representation [CL]

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http://arxiv.org/abs/2210.02800


We present an ab initio study of the rovibronic spectra of sulfur monoxide ($^{32}$S$^{16}$O) using internally contracted multireference confoguration interaction (ic-MRCI) method and aug-cc-pV5Z basis sets. It covers 13 electronic states $X^{3}\Sigma^{-}$, $a^{1}\Delta$, $b^{1}\Sigma^{+}$, $c^{1}\Sigma^{-}$, $A^{\prime\prime 3}\Sigma^{+}$, $A^{\prime 3}\Delta$, $A^{3}\Pi$, $B^{3}\Sigma^{-}$, $C^{3}\Pi$, $d^{1}\Pi$, $e^{1}\Pi$, $C^{\prime 3}\Pi$, and $(3)^{1}\Pi$ ranging up to 66800 cm$^{-1}$. The ab initio spectroscopic model includes 13 potential energy curves, 23 dipole and transition dipole moment curves, 23 spin-orbit curves, and 14 electronic angular momentum curves. A diabatic representation is built by removing the avoided crossings between the spatially degenerate pairs $C^{3}\Pi – C^{\prime 3}\Pi$ and $e^{1}\Pi – (3)^{1}\Pi$ through a property-based diabatisation method. We also present non-adiabatic couplings and diabatic couplings for these avoided crossing systems. All phases for our coupling curves are defined, and consistent, providing the first fully reproducible spectroscopic model of SO covering the wavelength range longer than 147 nm. Finally, an ab initio rovibronic spectrum of SO is computed.

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R. Brady, S. Yurchenko, G. Kim, et. al.
Fri, 7 Oct 22
22/62

Comments: 15 pages, 14 figures

A variational model for the hyperfine resolved spectrum of VO in its ground electronic state [CL]

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http://arxiv.org/abs/2210.02896


A variational model for the infra-red spectrum of VO is presented which aims to accurately predict the hyperfine structure within the VO $\mathrm{X}\,^4\Sigma^-$ electronic ground state. To give the correct electron spin splitting of the $\mathrm{X}\,^4\Sigma^-$ state, electron spin dipolar interaction within the ground state and the spin-orbit coupling between $\mathrm{X}\,^4\Sigma^-$ and two excited states, $\mathrm{A}\,^4\Pi$ and $\mathrm{1}\,^2\Sigma^+$, are calculated ab initio alongside hyperfine interaction terms. Four hyperfine coupling terms are explicitly considered: Fermi-contact interaction, electron spin-nuclear spin dipolar interaction, nuclear spin-rotation interaction and nuclear electric quadrupole interaction. These terms are included as part of a full variational solution of the nuclear-motion Schr\”odinger equation performed using program DUO, which is used to generate both hyperfine-resolved energy levels and spectra. To improve the accuracy of the model, ab initio curves are subject to small shifts. The energy levels generated by this model show good agreement with the recently derived empirical term values. This and other comparisons validate both our model and the recently developed hyperfine modules in DUO.

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Q. Qu, S. Yurchenko and J. Tennyson
Fri, 7 Oct 22
34/62

Comments: N/A

Energetic Electron Irradiations of Amorphous and Crystalline Sulphur-Bearing Astrochemical Ices [CL]

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http://arxiv.org/abs/2210.01119


Laboratory experiments have confirmed that the radiolytic decay rate of astrochemical ice analogues is dependent upon the solid phase of the target ice, with some crystalline molecular ices being more radio-resistant than their amorphous counterparts. The degree of radio-resistance exhibited by crystalline ice phases is dependent upon the nature, strength, and extent of the intermolecular interactions that characterise their solid structure. For example, it has been shown that crystalline CH3OH decays at a significantly slower rate when irradiated by 2 keV electrons at 20 K than does the amorphous phase due to the stabilising effect imparted by the presence of an extensive array of strong hydrogen bonds. These results have important consequences for the astrochemistry of interstellar ices and outer Solar System bodies, as they imply that the chemical products arising from the irradiation of amorphous ices (which may include prebiotic molecules relevant to biology) should be more abundant than those arising from similar irradiations of crystalline phases. In this present study, we have extended our work on this subject by performing comparative energetic electron irradiations of the amorphous and crystalline phases of the sulphur-bearing molecules H2S and SO2 at 20 K. We have found evidence for phase-dependent chemistry in both these species, with the radiation-induced exponential decay of amorphous H2S being more rapid than that of the crystalline phase, similar to the effect that has been previously observed for CH3OH. For SO2, two fluence regimes are apparent: a low-fluence regime in which the crystalline ice exhibits a rapid exponential decay while the amorphous ice possibly resists decay, and a high-fluence regime in which both phases undergo slow exponential-like decays.

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D. Mifsud, P. Herczku, R. Rácz, et. al.
Wed, 5 Oct 22
40/73

Comments: Published in Frontiers in Chemistry (open access)

The quasi bound spectrum of H2 [GA]

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http://arxiv.org/abs/2209.13380


We compute the radiative ro-vibrational emission spectrum of H2 involving quasibound states via a simple numerical method of resolution of the Schr\”odinger equation by introducing a modifed effective molecular potential. The comparison of the eigenvalues obtained with our approximation and other theoretical methods based on scattering resonance properties is excellent. Electric quadrupole and magnetic dipole contributions are calculated and we confirm the previous computations of Forrey of the electric quadrupole transition Einstein coeffcients. The astrophysical relevance of such quasibound levels is emphasized

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E. Roueff and H. Abgrall
Wed, 28 Sep 22
67/89

Comments: 10 pages,1 figure, 4 tables

FRECKLL: Full and Reduced Exoplanet Chemical Kinetics distiLLed [EPA]

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http://arxiv.org/abs/2209.11203


We introduce a new chemical kinetic code FRECKLL (Full and Reduced Exoplanet Chemical Kinetics distiLLed) to evolve large chemical networks efficiently. FRECKLL employs `distillation’ in computing the reaction rates, which minimizes the error bounds to the minimum allowed by double precision values ($\epsilon \leq 10^{-15}$). FRECKLL requires less than 5 minutes to evolve the full Venot2020 network in a 130 layers atmosphere and 30 seconds to evolve the Venot2020 reduced scheme. Packaged with FRECKLL is a TauREx 3.1 plugin for usage in forward modelling and retrievals. We present TauREx retrievals performed on a simulated HD189733 JWST spectra using the full and reduced Venot2020 chemical networks and demonstrate the viability of total disequilibrium chemistry retrievals and the ability for JWST to detect disequilibrium processes.

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A. Al-Refaie, O. Venot, Q. Changeat, et. al.
Fri, 23 Sep 22
30/70

Comments: 13 pages, 8 figures

The Role of High Energy Photoelectrons on the Dissociation of Molecular Nitrogen in Earth's Ionosphere [CL]

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http://arxiv.org/abs/2209.11185


Soft x-ray radiation from the sun is responsible for the production of high energy photoelectrons in the D and E regions of the ionosphere, where they deposit most of their ionization energy. The photoelectrons created by this process are the main drivers for dissociation of Nitrogen molecule ($N_2$) below 200 km. Furthermore, the dissociation of $N_2$ is one of main mechanisms of the production of Nitric Oxide (NO) at these altitudes. In order to estimate the dissociation rate of $N_2$ we need its dissociation cross-sections. The dissociation cross-sections for $N_2$ by photoelectrons are primarily estimated from the cross-sections of its excitation states using predissociation factors and dissociative ionization channels. Unfortunately, the lack of cross-sections data, particularly at high electron energies and of higher excited states of $N_2$ and $N_2^+$, introduces a lot of uncertainty in the dissociation rate calculation, which subsequently leads to uncertainties in the NO production rate from this source.

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S. Samaddar, K. Venkataramani, J. Yonker, et. al.
Fri, 23 Sep 22
39/70

Comments: N/A

Peptide Bonds in the Interstellar Medium: Facile Autocatalytic Formation from Nitriles on Water-Ice Grains [GA]

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http://arxiv.org/abs/2209.10929


A recent suggestion that acetamide, \ce{CH3C(O)NH2}, could be readily formed on water-ice grains by the acid induced addition of water across the \ce{CN} bond is now shown to be valid. Computational modelling of the reaction between \ce{R-CN} (R = H, \ce{CH3}) and a cluster of 32 molecules of water and one \ce{H3O+} proceeds auto-catalytically to form firstly a hydroxy imine \ce{R-C(OH)=NH} and secondly an amide \ce{R-C(O)NH2}. Quantum mechanical tunnelling, computed from small-curvature estimates, plays a key role in the rates of these reactions. This work represents the first credible effort to show how amides can be formed from abundant substrates, namely nitriles and water, reacting on a water-ice cluster containing catalytic amounts of hydrons in the interstellar medium with consequential implications towards the origins of life.

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B. Kerkeni and J. Simmie
Fri, 23 Sep 22
58/70

Comments: 19 pages, 8 Figures

An experimental and theoretical investigation of HCN production in the Hadean Earth atmosphere [EPA]

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http://arxiv.org/abs/2209.09257


A critical early stage for the origin of life on Earth may have involved the production of hydrogen cyanide (HCN) in a reducing, predominantly H$_2$ atmosphere. HCN is crucial for the origin of life as it is a possible precursor to several biomolecules that make up RNA and proteins including nucleobases, nucleotides, amino acids, and ribose. In this work, we perform an in depth experimental and theoretical investigation of HCN production in reducing atmospheric conditions (89-95% H$_2$) possibly representing the earliest stages of the Hadean eon, ~4.5-4.3 billion years ago. We make use of cold plasma discharges – a laboratory analog to shortwave UV radiation – to simulate HCN production in the upper layers of the atmosphere for CH$_4$ abundances ranging from 0.1-6.5%. We then combine experimental mass spectrum measurements with our theoretical plasma models to estimate the HCN concentrations produced in our experiments. We find that upper atmospheric HCN production scales linearly with CH$_4$ abundance with the relation [HCN] = 0.13 $\pm$ 0.01[CH$_4$]. Concentrations of HCN near the surface of the Hadean Earth are expected to be about 2-3 orders of magnitude lower. The addition of 1% water to our experiments results in a ~50% reduction in HCN production. We find that four reactions are primarily responsible for HCN production in our experiments: (i) $^4$N + CH$_3$ -> H$_2$CN + H -> HCN + H$_2$, (ii) $^4$N + CH -> CN + H followed by CN + CH$_4$ -> HCN + CH$_3$, (iii) C$_2$H$_4$ + $^4$N -> HCN + CH$_3$, and (iv) $^4$N + $^3$CH$_2$ -> HCN + H. The most prebiotically favorable Hadean atmosphere would have been very rich in CH$_4$ (> 5%), and as a result of greenhouse effects the surface would be likely very hot. In such a prebiotic scenario, it may have been important to incorporate HCN into organic hazes that could later release biomolecules and precursors into the first ponds.

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B. Pearce, C. He and S. Hörst
Wed, 21 Sep 22
16/68

Comments: Accepted for publication in ACS Earth and Space Chemistry, 24 pages, 7 figures, 5 tables, Supporting info

Trustworthy modelling of atmospheric formaldehyde powered by deep learning [CL]

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http://arxiv.org/abs/2209.07414


Formaldehyde (HCHO) is one one of the most important trace gas in the atmosphere, as it is a pollutant causing respiratory and other diseases. It is also a precursor of tropospheric ozone which damages crops and deteriorates human health. Study of HCHO chemistry and long-term monitoring using satellite data is important from the perspective of human health, food security and air pollution. Dynamic atmospheric chemistry models struggle to simulate atmospheric formaldehyde and often overestimate by up to two times relative to satellite observations and reanalysis. Spatial distribution of modelled HCHO also fail to match satellite observations. Here, we present deep learning approach using a simple super-resolution based convolutional neural network towards simulating fast and reliable atmospheric HCHO. Our approach is an indirect method of HCHO estimation without the need to chemical equations. We find that deep learning outperforms dynamical model simulations which involves complicated atmospheric chemistry representation. Causality establishing the nonlinear relationships of different variables to target formaldehyde is established in our approach by using a variety of precursors from meteorology and chemical reanalysis to target OMI AURA satellite based HCHO predictions. We choose South Asia for testing our implementation as it doesnt have in situ measurements of formaldehyde and there is a need for improved quality data over the region. Moreover, there are spatial and temporal data gaps in the satellite product which can be removed by trustworthy modelling of atmospheric formaldehyde. This study is a novel attempt using computer vision for trustworthy modelling of formaldehyde from remote sensing can lead to cascading societal benefits.

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M. Biswas and M. Singh
Fri, 16 Sep 22
30/84

Comments: N/A

Resilience of small PAHs in interstellar clouds: Efficient stabilization of cyanonaphthalene by fast radiative cooling [GA]

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http://arxiv.org/abs/2209.05229


After decades of speculation and searching, astronomers have recently identified specific Polycyclic Aromatic Hydrocarbons (PAHs) in space. Remarkably, the observed abundance of cyanonaphthalene (CNN, C10H7CN) in the Taurus Molecular Cloud (TMC-1) is six orders of magnitude higher than expected from astrophysical modeling. Here, we report absolute unimolecular dissociation and radiative cooling rate coefficients of the 1-CNN isomer in its cationic form. These results are based on measurements of the time-dependent neutral product emission rate and Kinetic Energy Release distributions produced from an ensemble of internally excited 1-CNN + studied in an environment similar to that in interstellar clouds. We find that Recurrent Fluorescence – radiative relaxation via thermally populated electronic excited states – efficiently stabilizes 1-CNN+ , owing to a large enhancement of the electronic transition probability by vibronic coupling. Our results help explain the anomalous abundance of CNN in TMC-1 and challenge the widely accepted picture of rapid destruction of small PAHs in space.

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M. Stockett, J. Bull, H. Cederquist, et. al.
Tue, 13 Sep 22
52/85

Comments: N/A

Current challenges in the physics of white dwarf stars [SSA]

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http://arxiv.org/abs/2209.02846


White dwarfs are a class of stars with unique physical properties. They present many challenging problems whose solution requires the application of advanced theories of dense matter, state-of-the-art experimental techniques, and extensive computing efforts. New ground- and space-based observatories will soon provide an increasingly detailed view of white dwarf stars and reveal new phenomena that will challenge our models. This review is an introduction for researchers who are not in the field of white dwarf astrophysics with the intent to entice them to contribute their expertise to advance our knowledge of these exotic stars. We discuss a wide variety of currently unsolved or partially resolved problems that are broadly related to equations of state, transport processes and opacities.

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D. Saumon, S. Blouin and P. Tremblay
Thu, 8 Sep 22
7/77

Comments: Review article to appear in Physics Reports. 108 pages of text, 33 figures, 372 references

The gas-phase reaction of NH2 with formaldehyde (CH2O) is not a source of formamide (NH2CHO) in interstellar environments [GA]

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http://arxiv.org/abs/2208.12658


The first experimental study of the low-temperature kinetics of the gas-phase reaction of NH2 with formaldehyde (CH2O) has been performed. This reaction has previously been suggested as a source of formamide (NH2CHO) in interstellar environments. A pulsed Laval nozzle equipped with laser-flash photolysis and laser-induced fluorescence spectroscopy was used to create and monitor the temporal decay of NH2 in the presence of CH2O. No loss of NH2 could be observed via reaction with CH2O and we place an upper-limit on the rate coefficient of <6×10-12 cm3 molecule-1 s-1 at 34K. Ab initio calculations of the potential energy surface were combined with RRKM calculations to predict a rate coefficient of 6.2×10-14 cm3 molecule-1 s-1 at 35K, consistent with the experimental results. The presence of a significant barrier, 18 kJ mol-1, for the formation of formamide as a product, means that only the H-abstraction channel producing NH3 + CHO, in which the transfer of an H-atom can occur by quantum mechanical tunnelling through a 23 kJ mol-1 barrier, is open at low temperatures. These results are in contrast with a recent theoretical study which suggested that the reaction could proceed without a barrier and was therefore a viable route to gas-phase formamide formation. The calculated rate coefficients were used in an astrochemical model which demonstrated that this reaction produces only negligible amounts of gas-phase formamide under interstellar and circumstellar conditions. The reaction of NH2 with CH2O is therefore not an important source of formamide at low temperatures in interstellar environments.

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K. Douglas, D. Lucas, C. Walsh, et. al.
Mon, 29 Aug 22
3/49

Comments: Manuscript, 14 pages, 4 figures. Supporting Information, 8 pages, 2 figures. Accepted for publication in The Astrophysical Journal Letters

Hyperfine resolved rate coefficients of HC17O+ with H2 (j = 0) [GA]

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http://arxiv.org/abs/2208.09850


The formyl cation (HCO+) is one of the most abundant ions in molecular clouds and plays a major role in the interstellar chemistry. For this reason, accurate collisional rate coefficients for the rotational excitation of HCO+ and its isotopes due to the most abundant perturbing species in interstellar environments are crucial for non-local thermal equilibrium models and deserve special attention. In this work, we determined the first hyperfine resolved rate coefficients of HC17O+ in collision with H2 (j=0). Indeed, despite no scattering calculations on its collisional parameters have been performed so far, the HC17O+ isotope assumes a prominent role for astrophysical modelling applications. Computations are based on a new four dimensional (4D) potential energy surface, obtained at the CCSD(T)-F12a/aug-cc-pVQZ level of theory. A test on the corresponding cross section values pointed out that, to a good approximation, the influence of the coupling between rotational levels of H2 can be ignored. For this reason, the H2 collider has been treated as a spherical body and an average of the potential based on five orientations of H2 has been employed for scattering calculations. State-to-state rate coefficients resolved for the HC17O+ hyperfine structure for temperature ranging from 5 to 100 K have been computed using recoupling techniques. This study provides the first determination of HC17O+/H2 inelastic rate coefficients directly computed from full quantum close-coupling equations, thus supporting the reliability of future radiative transfer modellings of HC17O+ in interstellar environments.

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F. Tonolo, F. Lique, M. Melosso, et. al.
Tue, 23 Aug 22
37/79

Comments: 9 pages, 6 figures

Studying the interaction between VUV photons and PAHs in relevant astrophysical conditions [IMA]

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http://arxiv.org/abs/2208.09175


PIRENEA and PIRENEA 2 are experimental setups dedicated to the study of fundamental molecular processes involving species of astrochemical interest. The coupling of a VUV source to PIRENEA has allowed us to study the fragmentation pathways and stability of polycyclic aromatic hydrocarbons (PAHs) containing aliphatic bonds under conditions relevant for astrophysical photodissociation regions. PIRE-NEA 2 will open the possibility to extend these studies to larger systems such as PAH clusters, and more generally to study gas-nanograin-photon interactions.

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A. Marciniak, A. Bonnamy, S. Zamith, et. al.
Mon, 22 Aug 22
29/53

Comments: Book Series: Astrophysics and Space Science Proceedings (ASSSP)

Carbon macromolecules in the cycle of interstellar matter: observations andlaboratory experiments [GA]

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http://arxiv.org/abs/2208.08167


Carbon macromolecules are intermediates between small gas-phase species and larger dust structures. I illustrate how observations and dedicated laboratory experiments support this picture.

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C. Joblin
Thu, 18 Aug 22
24/45

Comments: N/A

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

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http://arxiv.org/abs/2208.05203


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.

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C. Rocha, H. Linnartz and A. Varandas
Thu, 11 Aug 22
26/68

Comments: Accepted for publication in JCP

Infrared multiple-angle incidence resolution spectrometry for vapor-deposited amorphous water [IMA]

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http://arxiv.org/abs/2205.14547


Infrared (IR) multiple-angle incidence resolution spectrometry (IR-MAIRS) is a recently developed spectroscopic technique that combines oblique incidence transmission measurements and chemometrics (multivariate analysis) to obtain both pure in-plane (IP) and out-of-plane (OP) vibration spectra for a thin sample. IR-MAIRS is established for analyzing the molecular orientation of organic thin films at atmospheric pressure, but it should also be powerful for the structural characterization of vapor-deposited thin samples prepared in a vacuum. The application of IR-MAIRS to vapor-deposited amorphous water is particularly interesting in the fields of physical and interstellar chemistry, because it is a representative model material for interstellar icy dust grains. We recently developed an experimental setup for in situ IR-MAIRS under low-temperature, ultra-high-vacuum conditions, which thus facilitates measurements of interstellar ice analogues such as vapor-deposited amorphous water. This review considers the theoretical framework of IR-MAIRS and our recent experimental results for vapor-deposited amorphous water. We present spectroscopic signatures for the perpendicular orientation of dangling OH bonds for three-coordinated water molecules at the surface of amorphous water at 90 K. The absolute absorption cross-section of the three-coordinated dangling OH bonds is quantitatively measured. As IR-MAIRS can essentially be conducted using only a Fourier-transform IR spectrometer and an angle-controllable linear polarizer, it is a useful, low-cost, and simple spectroscopic technique for studying laboratory analogues of interstellar ices including vapor-deposited amorphous water.

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T. Nagasawa, N. Numadate and T. Hama
Tue, 31 May 22
66/89

Comments: N/A

Top-down formation of ethylene from fragmentation of superhydrogenated polycyclic aromatic hydrocarbons [GA]

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http://arxiv.org/abs/2205.07705


Fragmentation is an important decay mechanism for polycyclic aromatic hydrocarbons (PAHs) under harsh interstellar conditions and represents a possible formation pathway for small molecules such as H2, C2H2, C2H4. Our aim is to investigate the dissociation mechanism of superhydrogenated PAHs that undergo energetic processing and the formation pathway of small hydrocarbons. We obtain, experimentally, the mass distribution of protonated tetrahydropyrene (C16H15 , py+5H+) and protonated hexahydropyrene (C16H17+, py+7H+) upon collision induced dissociation (CID). The IR spectra of their main fragments are recorded by infrared multiple-photon dissociation (IRMPD). Extended tight-binding (GFN2-xTB) based molecular dynamics simulations are performed in order to provide the missing structure information in experiment and identify fragmentation pathways. The pathways for fragmentation are further investigated at a hybrid-density functional theory (DFT) and dispersion corrected level. A strong signal for loss of 28 mass units of py+7H+ is observed both in the CID experiment and the MD simulation, while py+5H+ shows negligible signal for the product corresponding to a mass loss of 28. The 28 mass loss from py+7H+ is assigned to the loss of ethylene (C2H4) and a good fit between the calculated and experimental IR spectrum of the resulting fragment species is obtained. Further DFT calculations show favorable kinetic pathways for loss of C2H4 from hydrogenated PAH configurations involving three consecutive CH2 molecular entities. This joint experimental and theoretical investigation proposes a chemical pathway of ethylene formation from fragmentation of superhydrogenated PAHs. This pathway is sensitive to hydrogenated edges (e.g. the degree of hydrogenation and the hydrogenated positions). The inclusion of this pathway in astrochemical models may improve the estimated abundance of ethylene.

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Z. Tang, F. Simonsen, R. Jaganathan, et. al.
Tue, 17 May 22
16/95

Comments: Accepted by Astronomy and Astrophysics

TEM analyses of in situ presolar grains from unequilibrated ordinary chondrite LL3.0 Semarkona [EPA]

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http://arxiv.org/abs/2205.04372


We investigated six presolar grains from very primitive regions of the matrix in the unequilibrated ordinary chondrite Semarkona with TEM. These grains include one SiC, one oxide (Mg-Al spinel), and four silicates. Structural and elemental compositional studies of presolar grains located within their meteorite hosts have the potential to provide information on conditions and processes throughout the grains’ histories. Our analyses show that the SiC and spinel grains are stoichiometric and well crystallized. In contrast, the majority of the silicate grains are non-stoichiometric and poorly crystallized. These findings are consistent with previous TEM studies of presolar grains from interplanetary dust particles and chondritic meteorites. We interpret the poorly crystalline nature, non-stoichiometry, more Fe- rather than Mg-rich compositions, and/or compositional heterogeneities as features of the formation by condensation under non-equilibrium conditions. Evidence for parent body alteration includes rims with mobile elements (S or Fe) on the SiC grain and one silicate grain. Other features characteristic of secondary processing in the interstellar medium, the solar nebula, and/or on parent bodies, were not observed or are better explained by processes operating in circumstellar envelopes. In general, there was very little overprinting of primary features of the presolar grains by secondary processes (e.g., ion irradiation, grain-grain collisions, thermal metamorphism, aqueous alteration). This finding underlines the need for additional TEM studies of presolar grains located in the primitive matrix regions of Semarkona, to address gaps in our knowledge of presolar grain populations accreted to ordinary chondrites.

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S. Singerling, L. Nittler, J. Barosch, et. al.
Tue, 10 May 22
54/70

Comments: 50 pages including supplementary materials

Vertical distribution of cyclopropenylidene and propadiene in the atmosphere of Titan [EPA]

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http://arxiv.org/abs/2204.13064


Titan’s atmosphere is a natural laboratory for exploring the photochemical synthesis of organic molecules. Significant recent advances in the study of the atmosphere of Titan include: (a) detection of C$_3$ molecules: C$_3$H$_6$, CH$_2$CCH$_2$, c-C$_3$H$_2$, and (b) retrieval of C$_6$H$_6$, which is formed primarily via C$_3$ chemistry, from Cassini-UVIS data. The detection of $c$-C$_3$H$_2$ is of particular significance since ring molecules are of great astrobiological importance. Using the Caltech/JPL KINETICS code, along with the best available photochemical rate coefficients and parameterized vertical transport, we are able to account for the recent observations. It is significant that ion chemistry, reminiscent of that in the interstellar medium, plays a major role in the production of c-C$_3$H$_2$ above 1000 km.

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K. Willacy, S. Chen, D. Adams, et. al.
Thu, 28 Apr 22
56/70

Comments: 18 pages (+ 27 page appendix), 16 figures

A missing link in the nitrogen-rich organic chain on Titan [EPA]

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http://arxiv.org/abs/2204.11281


Context. The chemical building blocks of life contain a large proportion of nitrogen, an essential element. Titan, the largest moon of Saturn, with its dense atmosphere of molecular nitrogen and methane, offers an exceptional opportunity to explore how this element is incorporated into carbon chains through atmospheric chemistry in our Solar System. A brownish dense haze is consistently produced in the atmosphere and accumulates on the surface on the moon. This solid material is nitrogen-rich and may contain prebiotic molecules carrying nitrogen. Aims. To date, our knowledge of the processes leading to the incorporation of nitrogen into organic chains has been rather limited. In the present work, we investigate the formation of nitrogen-bearing ions in an experiment simulating Titan s upper atmosphere, with strong implications for the incorporation of nitrogen into organic matter on Titan. Methods. By combining experiments and theoretical calculations, we show that the abundant N2+ ion, produced at high altitude by extreme-ultraviolet solar radiation, is able to form nitrogen-rich organic species. Results. An unexpected and important formation of CH3N2+ and CH2N2+ diazo-ions is experimentally observed when exposing a gas mixture composed of molecular nitrogen and methane to extreme-ultraviolet radiation. Our theoretical calculations show that these diazo-ions are mainly produced by the reaction of N2+ with CH3 radicals. These small nitrogen-rich diazo-ions, with a N/C ratio of two, appear to be a missing link that could explain the high nitrogen content in Titan s organic matter. More generally, this work highlights the importance of reactions between ions and radicals, which have rarely been studied thus far, opening up new perspectives in astrochemistry.

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N. Carrasco, J. Bourgalais, L. Vettier, et. al.
Tue, 26 Apr 22
58/74

Comments: N/A

Anthropic constraint on transient variations of fundamental constants [CL]

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http://arxiv.org/abs/2202.04228


The anthropic principle implies that life can emerge and be sustained only in a narrow range of values of fundamental constants (FCs). We extend the anthropic arguments to a regime of transient variations of FCs. Such regime is characteristic of clumpy dark matter models where inside the clumps FCs can reach values vastly different from their everyday values. We show that the passage of such a macroscopic clump through Earth would make Earth uninhabitable. The periodic table of elements is truncated and water fails to serve as a universal solvent. Anthropic principle enables us to improve existing astrophysical bounds on certain dark matter model couplings by five orders of magnitude.

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V. Dergachev, H. Tan, S. Varganov, et. al.
Mon, 25 Apr 22
31/36

Comments: 16 pages, 14 figures

Possible Ribose Synthesis in Carbonaceous Planetesimals [CL]

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http://arxiv.org/abs/2204.06523


The origin of life might be sparked by the polymerization of the first RNA molecules in Darwinian ponds during wet-dry cycles. The key life-building block ribose was found in carbonaceous chondrites. Its exogenous delivery onto the Hadean Earth could be a crucial step toward the emergence of the RNA world. Here, we investigate the formation of ribose through a simplified version of the formose reaction inside carbonaceous chondrite parent bodies. Following up on our previous studies regarding nucleobases with the same coupled physico-chemical model, we calculate the abundance of ribose within planetesimals of different sizes and heating histories. We perform laboratory experiments using catalysts present in carbonaceous chondrites to infer the yield of ribose among all pentoses (5Cs) forming during the formose reaction. These laboratory yields are used to tune our theoretical model that can only predict the total abundance of 5Cs. We found that the calculated abundances of ribose were similar to the ones measured in carbonaceous chondrites. We discuss the possibilities of chemical decomposition and preservation of ribose and derived constraints on time and location in planetesimals. In conclusion, the aqueous formose reaction might produce most of the ribose in carbonaceous chondrites. Together with our previous studies on nucleobases, we found that life-building blocks of the RNA world could be synthesized inside parent bodies and later delivered onto the early Earth.

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K. Paschek, K. Kohler, B. Pearce, et. al.
Thu, 14 Apr 22
39/62

Comments: Published in Life, 24 pages, 8 figures (all colored)

Gliding on ice in search of accurate and cost-effective computational methods for astrochemistry on grains: the puzzling case of the HCN isomerization [CL]

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http://arxiv.org/abs/2204.04642


The isomerization of hydrogen cyanide to hydrogen isocyanide on icy grain surfaces is investigated by an accurate composite method (jun-Cheap) rooted in the coupled cluster ansatz and by density functional approaches. After benchmarking density functional predictions of both geometries and reaction energies against jun-Cheap results for the relatively small model system HCN — (H2O)2 the best performing DFT methods are selected. A large cluster containing 20 water molecules is then employed within a QM/QM$’$ approach to include a realistic environment mimicking the surface of icy grains. Our results indicate that four water molecules are directly involved in a proton relay mechanism, which strongly reduces the activation energy with respect to the direct hydrogen transfer occurring in the isolated molecule. Further extension of the size of the cluster up to 192 water molecules in the framework of a three-layer QM/QM’/MM model has a negligible effect on the energy barrier ruling the isomerization. Computation of reaction rates by transition state theory indicates that on icy surfaces the isomerization of HNC to HCN could occur quite easily even at low temperatures thanks to the reduced activation energy that can be effectively overcome by tunneling.

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C. Baiano, J. Lupi, V. Barone, et. al.
Tue, 12 Apr 22
41/87

Comments: Accepted on JCTC

$δ^{44/40}$Ca-$δ^{88/86}$Sr multi-proxy constrains primary origin of Marinoan cap carbonates [CL]

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http://arxiv.org/abs/2204.02563


The Neoproterozoic Earth experienced at least two global-scale glaciations termed Snowball Earth events. ‘Cap carbonates’ were widely deposited after the events, but controversy surrounds their origin. Here, we apply the novel $\delta^{44/40}$Ca-$\delta^{88/86}$Sr multi-proxy to two Marinoan (ca. 635 Ma) cap carbonate sequences from Namibia and show that the rocks archive primary environmental signals deriving from a combination of seawater-glacial meltwater mixing and kinetic isotope effects. In an outer platform section, dolostone $\delta^{44/40}$Ca and $\delta^{88/86}$Sr values define a line predicted for kinetic mass-dependent isotope fractionation. This dolostone mostly precipitated from meltwater. Moreover, stratigraphically higher samples exhibiting the fastest precipitation rates correlate with elevated 87Sr/86Sr ratios, consistent with long-held expectations that a rapid deglacial weathering pulse forced cap carbonate formation. An inner-platform dolostone shows greater effects from water-mass mixing but still reveals that precipitation rates increased up-section. Overlying limestones show the greatest Ca and Sr contributions from seawater. Amplification of local coastal processes during global ice sheet collapse offers a simple but sufficient proposition to explain the Ca isotope heterogeneity of cap carbonates. Detection of kinetic isotope effects in the rock record provides a basis for developing the $\delta^{44/40}$Ca-$\delta^{88/86}$Sr multi-proxy as an indicator of saturation state and $p$CO$_2$.

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J. Wang, A. Jacobson, B. Sageman, et. al.
Thu, 7 Apr 22
26/45

Comments: N/A

Precursors of the RNA-world in space: Detection of ($Z$)-1,2-ethenediol in the interstellar medium, a key intermediate in sugar formation [GA]

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http://arxiv.org/abs/2203.14728


We present the first detection of ($Z$)-1,2-ethenediol, (CHOH)$_2$, the enol form of glycolaldehyde, in the interstellar medium towards the G+0.693-0.027 molecular cloud located in the Galactic Center. We have derived a column density of (1.8$\pm$0.1)$\times$10$^{13}$ cm$^{-2}$, which translates into a molecular abundance with respect to molecular hydrogen of 1.3$\times$10$^{-10}$. The abundance ratio between glycolaldehyde and ($Z$)-1,2-ethenediol is $\sim$5.2. We discuss several viable formation routes through chemical reactions from precursors such as HCO, H$_2$CO, HCOH or CH$_2$CHOH. We also propose that this species might be an important precursor in the formation of glyceraldehyde (HOCH$_2$CHOHCHO) in the interstellar medium through combination with the hydroxymethylene (CHOH) radical.

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V. Rivilla, L. Colzi, I. Jiménez-Serra, et. al.
Tue, 29 Mar 22
68/73

Comments: Accepted for publication in The Astrophysical Journal Letters

Chiral 480nm absorption in the hemoglycin space polymer [CL]

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http://arxiv.org/abs/2203.06130


A 1494 Dalton hemoglycin space polymer of Glycine18 Hydroxy-glycine4 Fe2O4 termed the core unit is part of a polymer of Glycine, Si, Fe and O that forms tubes, vesicles and a lattice structure isolated from CV3 meteorites and characterized by mass spectrometry, FIB/SIMS and X-ray analysis. In Hartree-Fock calculations the polymer has an absorption of blue light at 480nm that is dependent on rectus R (= dextro D) chirality in a hydroxy-glycine residue whose C-terminus is bonded to an iron atom. The absorption originates in the Fe II state as a consequence of chiral symmetry breaking. The infrared spectrum is presented. We discuss how the core unit could have been selected 4.5 billion years ago in our protoplanetary disc by blue light from the early sun.

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J. McGeoch and M. McGeoch
Mon, 14 Mar 22
47/67

Comments: 14 pages, 8 figures, 2 tables

Electron-induced excitation, recombination and dissociation of molecular ions initiating the formation of complex organic molecules [CL]

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http://arxiv.org/abs/2203.05441


We review the study of dissociative recombination and ro-vibrational excitation of diatomic and small polyatomic molecular ions initiating complex organic molecules formation. In particular, we show how Multichannel Quantum Defect Theory (MQDT) and R-matrix methods are used to compute cross sections and rate coefficients for cations in well defined ro-vibrational levels of the ground electronic state, from sub-meV up to few eV collision energies.
The most recent MQDT results are compared with either other theoretical data, or with measured data obtained in storage-ring experiments.

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J. Mezei, K. Chakrabarti, M. Epée, et. al.
Fri, 11 Mar 22
2/59

Comments: 20 pages, 13 figures

Mid-IR and VUV Spectroscopic Characterisation of Thermally Processed and Electron Irradiated CO2 Astrophysical Ice Analogues [GA]

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http://arxiv.org/abs/2203.02847


The astrochemistry of CO2 ice analogues has been a topic of intensive investigation due to the prevalence of CO2 throughout the interstellar medium and the Solar System, as well as the possibility of it acting as a carbon feedstock for the synthesis of larger, more complex organic molecules. In order to accurately discern the physico-chemical processes in which CO2 plays a role, it is necessary to have laboratory-generated spectra to compare against observational data acquired by ground- and space-based telescopes. A key factor which is known to influence the appearance of such spectra is temperature, especially when the spectra are acquired in the infrared and ultraviolet. In this present study, we describe the results of a systematic investigation looking into: (i) the influence of thermal annealing on the mid-IR and VUV absorption spectra of pure, unirradiated CO2 astrophysical ice analogues prepared at various temperatures, and (ii) the influence of temperature on the chemical products of electron irradiation of similar ices. Our results indicate that both mid-IR and VUV spectra of pure CO2 ices are sensitive to the structural and chemical changes induced by thermal annealing. Furthermore, using mid-IR spectroscopy, we have successfully identified the production of radiolytic daughter molecules as a result of 1 keV electron irradiation and the influence of temperature over this chemistry. Such results are directly applicable to studies on the chemistry of interstellar ices, comets, and icy lunar objects and may also be useful as reference data for forthcoming observational missions.

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D. Mifsud, Z. Kaňuchová, S. Ioppolo, et. al.
Tue, 8 Mar 22
76/100

Comments: Published in the ‘Journal of Molecular Spectroscopy’. Includes 40 pages, 7 figures, 2 tables, and a graphical abstract

Surface astrochemistry: a computational chemistry perspective [GA]

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http://arxiv.org/abs/2202.04992


Molecules in space are synthesized via a large variety of gas-phase reactions, and reactions on dust-grain surfaces, where the surface acts as a catalyst. Especially, saturated, hydrogen-rich molecules are formed through surface chemistry. Astrochemical models have developed over the decades to understand the molecular processes in the interstellar medium, taking into account grain surface chemistry. However, essential input information for gas-grain models, such as binding energies of molecules to the surface, have been derived experimentally only for a handful of species, leaving hundreds of species with highly uncertain estimates. Moreover, some fundamental processes are not well enough constrained to implement these into the models.
The proceedings gives three examples how computational chemistry techniques can help answer fundamental questions regarding grain surface chemistry.

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H. Cuppen, A. Fredon, T. Lamberts, et. al.
Fri, 11 Feb 22
13/71

Comments: (12 pages, 8 figures)

Rotational spectroscopy of isotopic oxirane, $c$-C$_2$H$_4$O [CL]

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http://arxiv.org/abs/2201.09266


We studied the rotational spectrum of oxirane in a sample of natural isotopic composition in selected regions between 158 GHz and 1093 GHz. Investigations of the isotopologs with one $^{13}$C or one $^{18}$O were the primary focus in order to facilitate searches for them in space. We also examined the main isotopic species mainly to look into the performance of Watson’s A and S reductions both in an oblate and in a prolate representation. Even though oxirane is a rather asymmetric oblate rotor, the A reduction in the III$^l$ representation did not yield a satisfactory fit, as was observed frequently earlier for other molecules. The other three combinations yielded satisfactory fits of similar quality among each other; the A reduction in the I$^r$ representation required two parameters less than both S reduction fits.

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H. Müller, J. Guillemin, F. Lewen, et. al.
Tue, 25 Jan 22
33/78

Comments: 10 pages, including tables and figure; J. Mol. Spectrosc., accepted

The mid-UV spectrum of irradiated NaCl at Europa-like conditions [EPA]

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http://arxiv.org/abs/2201.01335


Recent observations from the Hubble Space Telescope show a mid-UV absorption feature localized to leading hemisphere chaos regions on Europa. The same regions were previously found to have a visible absorption at 450 nm that was attributed to the presence of irradiated NaCl. The lack of any additional diagnostic absorptions for NaCl in the visible spectrum of these terrains made confirmation of this identification difficult. Here we use laboratory experiments to show that NaCl irradiated at Europa’s surface temperatures develops an absorption at $\sim$220 nm consistent with the new detection in Europa’s mid-UV spectrum, strongly supporting the NaCl identification. Irradiated NaCl in leading-hemisphere chaos terrain would suggest that sodium and chlorine are important components of Europa’s subsurface ocean.

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M. Brown, W. Denman and S. Trumbo
Thu, 6 Jan 22
9/56

Comments: Planetary Science Journal, in press

The Influence of Temperature and Photobleaching on Irradiated Sodium Chloride at Europa-like Conditions [EPA]

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http://arxiv.org/abs/2201.01332


Europa’s leading hemisphere chaos regions have a spectral feature at 450 nm that has been attributed to absorption by crystal defects in irradiated sodium chloride, known as F-centers. Some discrepancies exist between the laboratory data of irradiated sodium chloride and the observations, including a $\sim$10 nm shift in central wavelength of the F-center band and the lack of the prominent 720 nm absorption on Europa from M-centers, which result from the coalescence of pairs of F-centers. Here, we perform irradiation experiments on sodium chloride in an attempt to understand these discrepancies. We show that careful control of the temperature of the sample at a temperature of 120 K yields F-centers with an absorption wavelength comparable to that of Europa. In addition, we measure the effect of photobleaching — the destruction of F-centers by photons — and show that at the energetic particle and photon flux on Europa, an equilibrium will be reached where only a modest F-center absorption develops. The density of F-centers never reaches high enough values for the creation of secondary M-centers. Our experiments predict that F-centers grow during the night on Europa in the absence of photobleaching and then partially decay during the daytime. We show observations from the Hubble Space Telescope consistent with this prediction. All observations of the 450 nm F-center on Europa are now consistent with laboratory measurements of sodium chloride, confirming the presence of this salt on Europa.

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W. Denman, S. Trumbo and M. Brown
Thu, 6 Jan 22
52/56

Comments: 11 pages, 8 figures, Published in conjunction with two other manuscripts, Planetary Science Journal, in press

Towards RNA life on Early Earth: From atmospheric HCN to biomolecule production in warm little ponds [EPA]

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http://arxiv.org/abs/2201.00829


The origin of life on Earth involves the early appearance of an information-containing molecule such as RNA. The basic building blocks of RNA could have been delivered by carbon-rich meteorites, or produced in situ by processes beginning with the synthesis of hydrogen cyanide (HCN) in the early Earth’s atmosphere. Here, we construct a robust physical and non-equilibrium chemical model of the early Earth atmosphere. The atmosphere is supplied with hydrogen from impact degassing of meteorites, sourced with water evaporated from the oceans, carbon dioxide from volcanoes, and methane from undersea hydrothermal vents, and in which lightning and external UV-driven chemistry produce HCN. This allows us to calculate the rain-out of HCN into warm little ponds (WLPs). We then use a comprehensive sources and sinks numerical model to compute the resulting abundances of nucleobases, ribose, and nucleotide precursors such as 2-aminooxazole resulting from aqueous and UV-driven chemistry within them. We find that at 4.4 bya (billion years ago) peak adenine concentrations in ponds can be maintained at ~2.8$\mu$M for more than 100 Myr. Meteorite delivery of adenine to WLPs produce similar peaks in concentration, but are destroyed within months by UV photodissociation, seepage, and hydrolysis. The early evolution of the atmosphere is dominated by the decrease of hydrogen due to falling impact rates and atmospheric escape, and the rise of oxygenated species such as OH from H2O photolysis. Our work points to an early origin of RNA on Earth within ~200 Myr of the Moon-forming impact.

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B. Pearce, K. Molaverdikhani, R. Pudritz, et. al.
Wed, 5 Jan 22
14/54

Comments: Accepted to ApJ, 27 pages (14 main text), 11 figures, 9 tables

Extensive Quantum Chemistry Study of Neutral and Charged C$_4$N Chains. An Attempt to Aid Astronomical Observation [CL]

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http://arxiv.org/abs/2112.09285


Many molecular species can presumably still be observed in space if they are adequately characterized chemically. In this paper, we suggest that this could be the case of the neutral (C$_4$N$^0$) and anion (C$_4$N$^-$) cyanopropynylidene chains, which were not yet identified in space although both the neutral (C$_3$N$^0$ and C$_5$N$^0$) and anion (C$_3$N$^-$} and C$_5$N$^-$) neighboring members of the homologous series were observed. Extensive data obtained from quantum chemical calculations using density functional theory (DFT), coupled cluster (CC), and quadratic configuration interaction (QCI) methods for all charge and spin states of interest for space science (doublet and quartet neutrals, triplet and singlet anions, and singlet and triplet cations) are reported: e.g., bond metric and natural bond order data, enthalpies of formation, dissociation and reaction energies, spin gaps, rotational constants, vibrational properties, dipole and quadrupole momenta, electron attachment energies ($EA$) and ionization potentials ($IP$). The fact that (not only for C$_4$N but also for C$_2$N and C$_6$N) the quantum chemical methods utilized here are able to excellently reproduce the experimental $EA$ value — which is often a challenge for theory — is particularly encouraging, since this indicates that theoretical estimates of chemical reactivity indices (which are key input parameters for modeling astrochemical evolution) can be trusted. The presently calculated enthalpies of formation and dissociation energies do not substantiate any reason to assume that C$_4$N is absent in space. To further support this idea, we analyze potential chemical pathways of formation of both C$_4$N$^0$ and C$_4$N$^-$, which include association and exchange reactions.

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I. Baldea
Mon, 20 Dec 21
45/59

Comments: N/A

(Sub-)millimeter-wave spectroscopy of gauche-propanal [CL]

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http://arxiv.org/abs/2112.04945


A detailed analysis of (sub-)millimeter-wave spectra of the vibrational ground state ($\upsilon=0$) combined with the energetically lowest excited vibrational state ($\upsilon_{24}=1$; aldehyde torsion) of gauche-propanal (g-C$2$H$_5$CHO) up to 500 GHz is presented. Both vibrational states, $\upsilon=0$ and $\upsilon{24}=1$, are treated with tunneling rotation interactions between their two respective tunneling states, which originate from two stable degenerate gauche-conformers; left- and right-handed configurations separated by a small potential barrier. Thanks to double-modulation double-resonance (DM-DR) measurements, important but weak $c$-type transitions connecting the tunneling states could be unambiguously assigned. In addition, Coriolis interaction as well as Fermi resonance between the two vibrational states needed to be taken into account to derive fits with experimental accuracy using Pickett’s SPFIT program in a reduced axis system (RAS). Based on the rotational analysis, the fundamental vibrational frequency $\nu_{24}$ of gauche-propanal is redetermined to 68.75037(30) cm$^{-1}$.

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O. Zingsheim, H. Müller, L. Bonah, et. al.
Fri, 10 Dec 21
5/94

Comments: accepted manuscript by Journal of Molecular Spectroscopy; 16 pages (11 main paper + 5 SM); 12 Figures (8+4)

Branching ratio for $\text{O}+\text{H}_3^+$ forming $\text{OH}^+ +\text{H}_2$ and $\text{H}_2\text{O}^+ +\text{H}$ [IMA]

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http://arxiv.org/abs/2112.04925


The gas-phase reaction of $\mathrm{O}+\mathrm{H}_3^+$ has two exothermic product channels, $\mathrm{OH}^+ +\mathrm{H}_2$ and $\mathrm{H}_2\mathrm{O}^+ +\mathrm{H}$. In the present study, we analyze experimental data from a merged-beams measurement to derive thermal rate coefficients resolved by product channel for the temperature range from 10 to 1000 K. Published astrochemical models either ignore the second product channel or apply a temperature-independent branching ratio of 70% vs. 30% for the formation of $\mathrm{OH}^+ +\mathrm{H}_2$ vs. $\mathrm{H}_2\mathrm{O}^+ +\mathrm{H}$, respectively, which originates from a single experimental data point measured at 295 K. Our results are consistent with this data point, but show a branching ratio that varies with temperature reaching 58% vs. 42% at 10 K. We provide recommended rate coefficients for the two product channels for two cases, one where the initial fine-structure population of the O$(^3P_J)$ reactant is in its $J=2$ ground state and the other one where it is in thermal equilibrium.

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P. Hillenbrand, N. Ruette, X. Urbain, et. al.
Fri, 10 Dec 21
21/94

Comments: 7 pages, 2 figures, 2 tables

The trans/cis ratio of formic, HCOOH, and thioformic, HC(O)SH, acids in the Interstellar Medium [GA]

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http://arxiv.org/abs/2111.10842


We studied theoretically the cis-trans isomerization reactions of two astrophysically relevant acids, formic acid (HCOOH) and thioformic acid (HC(O)SH), where the latter has recently been discovered in space. We also searched for these molecules towards the hot core G31.41+0.31 to compare their abundances with the expected theoretical isomerization results. Our results demonstrate that these isomerizations are viable in the conditions of the ISM due to ground-state tunneling effects, which allow the system to reach the thermodynamic equilibrium at moderately low temperatures. At very low temperatures (Tkin 10 K), the reaction rate constants for the cis to trans isomerizations are very small, which implies that the cis isomers should not be formed under cold ISM conditions. This is in disagreement with observations of the cis/trans isomers of HCOOH in cold cores where the cis isomer is found to be 5-6% the trans isomer. At high temperatures (150-300 K), our theoretical data not only match the observed behaviour of the trans/cis abundance ratios for HCOOH (the cis form is undetected), but they support our tentative detection of the trans and, for the first time in the insterstellar medium, of the cis isomer of HC(O)SH towards the hot molecular core G31.41+0.31 (with a measured trans/cis abundance ratio of 3.7). While the trans/cis ratio for HC(O)SH in the ISM depends on the relative stability of the isomers, the trans/cis ratio for HCOOH cannot be explained by isomerization, and it is determined by other competitive chemical processes

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J. Concepción, L. Colzi, I. Jiménez-Serra, et. al.
Tue, 23 Nov 21
38/84

Comments: 14 pages, 7 figures, 5 tables

Rotational and rovibrational spectroscopy of CD$_3$OH with an account of CD$_3$OH toward IRAS 16293$-$2422 [GA]

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http://arxiv.org/abs/2111.09055


Solar-type protostars harbor highly deuterated complex organics. While this degree of deuteration may provide important clues in studying the formation of these species, spectroscopic information on multiply deuterated isotopologs is often insufficient. In particular, searches for triply deuterated methanol, CD$_3$OH, are hampered by the lack of intensity information from a spectroscopic model. The aim of the present study is to develop such a model of CD$_3$OH in low-lying torsional states that is sufficiently accurate to facilitate further searches for CD$_3$OH in space. We performed a new measurement campaign for CD$_3$OH involving three spectroscopic laboratories that covers the 34 GHz-1.1 THz and the 20-900 cm$^{-1}$ ranges. The analysis was performed using the torsion-rotation Hamiltonian model based on the rho-axis method. We determined a model that describes the ground and first excited torsional states of CD$_3$OH, up to quantum numbers $J \leqslant 55$ and $K_a \leqslant 23$, and we derived a line list for radio-astronomical observations. This list is accurate up to at least 1.1 THz and should be sufficient for all types of radio-astronomical searches for this methanol isotopolog. It was used to search for CD$_3$OH in data from the Protostellar Interferometric Line Survey of IRAS 16293-2422 using ALMA. CD$_3$OH is securely detected in the data, with a large number of clearly separated and well-reproduced lines. We detected lines belonging to the ground and the first excited torsional states. The derived abundance of CD$_3$OH relative to non-deuterated isotopolog confirm the significant enhancement of this multiply deuterated variant. This finding is in line with other observations of multiply deuterated complex organic molecules and may serve as an important constraint on their formation models.

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V. Ilyushin, H. Müller, J. Jørgensen, et. al.
Thu, 18 Nov 21
39/92

Comments: Astronomy and Astrophysics, in press. 21 pages, including figures, tables, and appendices; abstract shortened

Gas-phase spectroscopy of photostable PAH ions from the mid- to far-infrared [CL]

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http://arxiv.org/abs/2111.08592


We present gas-phase InfraRed Multiple Photon Dissociation (IRMPD) spectroscopy of cationic phenanthrene, pyrene, and perylene over the 100$-$1700 cm$^{-1}$ (6-95 $\mu$m) spectral range. This range covers both local vibrational modes involving C$-$C and C$-$H bonds in the mid-IR, and large-amplitude skeletal modes in the far-IR. The experiments were done using the 7T Fourier-Transform Ion Cyclotron Resonance (FTICR) mass spectrometer integrated in the Free-Electron Laser for Intra-Cavity Experiments (FELICE), and findings were complemented with Density Functional Theory (DFT) calculated harmonic and anharmonic spectra, matching the experimental spectra well. The experimental configuration that enables this sensitive spectroscopy of the strongly-bound, photo-resistant Polycyclic Aromatic Hydrocarbons (PAHs) over a wide range can provide such high photon densities that even combination modes with calculated intensities as low as 0.01 km$\cdot$mol$^{-1}$ near 400 cm$^{-1}$ (25 $\mu$m) can be detected. Experimental frequencies from this work and all currently available IRMPD spectra for PAH cations were compared to theoretical frequencies from the NASA Ames PAH IR Spectroscopic Database to verify predicted trends for far-IR vibrational modes depending on PAH shape and size, and only a relatively small redshift (6$-$11 cm$^{-1}$) was found between experiment and theory. The absence of spectral congestion and the drastic reduction in bandwidth with respect to the mid-IR make the far-IR fingerprints viable candidates for theoretical benchmarking, which can aid in the search for individual large PAHs in the interstellar medium.

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S. Wiersma, A. Candian, J. Bakker, et. al.
Wed, 17 Nov 21
47/64

Comments: to be submitted to the Monthly Notices of the Royal Astronomical Society

C60 Cation as the Carrier of the 9577 and 9632 Angstrom Diffuse Interstellar Bands: Further Support from the VLT/X-Shooter Spectra [GA]

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http://arxiv.org/abs/2111.05769


Ever since their first detection over 100 years ago, the mysterious diffuse interstellar bands (DIBs), a set of several hundred broad absorption features seen against distant stars in the optical and near infrared wavelength range, largely remain unidentified. The close match both in wavelengths and in relative strengths recently found between the experimental absorption spectra of gas-phase buckminsterfullerene ions (C60+) and four DIBs at 9632, 9577, 9428 and 9365 Angstrom (and, to a lesser degree, a weaker DIB at 9348 Angstrom) suggests C60+ as a promising carrier. However, arguments against the C60+ identification remain and are mostly concerned with the large variation in the intensity ratios of the 9632 and 9577 DIBs. In this work, we search for these DIBs in the ESO VLT/X-shooter archival data and identify the 9632, 9577, 9428 and 9365 Angstrom DIBs in a sample of 25 stars. While the 9428 and 9365 Angstrom DIBs are too noisy to allow any reliable analysis, the 9632 and 9577 Angstrom DIBs are unambiguously detected and, after correcting for telluric water vapor absorption, their correlation can be used to probe their origin. To this end, we select a sub-sample of nine hot, O- or B0-type stars of which the stellar Mg II contamination to the 9632 Angstrom DIB is negligibly small. We find their equivalent widths, after normalized by reddening to eliminate their common correlation with the density of interstellar clouds, exhibit a tight, positive correlation. This supports C60+ as the carrier of the 9632 and 9577 Angstrom DIBs.

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T. Nie, F. Xiang and A. Li
Thu, 11 Nov 21
51/60

Comments: 8 pages, 4 figures, 2 tables; accepted for publication in the Monthly Notices of the Royal Astronomical Society

ExoMol line lists — XLIV. IR and UV line list for silicon monoxide (SiO) [EPA]

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http://arxiv.org/abs/2111.04859


A new silicon monoxide ($^{28}$Si$^{16}$O) line list covering infrared, visible and ultraviolet regions called SiOUVenIR is presented. This line list extends the infrared EBJT ExoMol line list by including vibronic transitions to the $A\,{}^{1}\Pi$ and $E\,{}^{1}\Sigma^{+}$ electronic states. Strong perturbations to the $A\,{}^{1}\Pi$ band system are accurately modelled through the treatment of 6 dark electronic states: $C\,{}^{1}\Sigma^{-}$, $D\,{}^{1}\Delta$, $a\,{}^{3}\Sigma^{+}$, $b\,{}^{3}\Pi$, $e\,{}^{3}\Sigma^{-}$ and $d\,{}^{3}\Delta$. Along with the $X\,{}^{1}\Sigma^{+}$ ground state, these 9 electronic states were used to build a comprehensive spectroscopic model of SiO using a combination of empirical and ab initio curves, including the potential energy (PE), spin-orbit (SO), electronic angular momentum (EAM) and (transition) dipole moment curves. The ab initio PE and coupling curves, computed at the multireference configuration interaction (MRCI) level of theory, were refined by fitting their analytical representations to 2617 experimentally derived SiO energy levels determined from 97 vibronic bands belonging to the $X$-$X$, $E$-$X$ and $A$-$X$ electronic systems through the MARVEL procedure. 112 observed forbidden transitions from the $C$-$X$, $D$-$X$, $e$-$X$, and $d$-$X$ bands were assigned using our predictions, and these could be fed back into the MARVEL procedure. The SiOUVenIR line list was computed using published ab initio transition dipole moments for the $E$-$X$ and $A$-$X$ bands; the line list is suitable for temperatures up to 10,000 K and for wavelengths longer than 140 nm. SiOUVenIR is available from www.exomol.com and the CDS database.

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S. Yurchenko, J. Tennyson, A. Syme, et. al.
Wed, 10 Nov 21
63/63

Comments: N/A

Trajectory-based simulation of far-infrared CIA profiles of CH$_4-$N$_2$ for modeling Titan's atmosphere [EPA]

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http://arxiv.org/abs/2111.02312


We report the results of the trajectory-based simulation of far-infrared collision-induced absorption (CIA) due to CH$_4-$N$_2$ pairs at temperatures between 70 and 400 K. Our analysis utilizes recently calculated high-level potential energy (PES) and induced dipole surfaces (IDS) [Finenko, A. A., Chistikov, D. N., Kalugina, Y. N., Conway E. K., Gordon, I. E., Phys. Chem. Chem. Phys., 2021, doi: 10.1039/d1cp02161c]. Treating collision partners as rigid rotors, the time evolution of interaction-induced dipole is accumulated over a vast ensemble of classical trajectories and subsequently transformed into CIA spectrum via Fourier transform. In our calculations, both bound and unbound states are properly accounted for, and the rigorous theory of lower-order spectral moments is addressed to check the accuracy of simulated profiles. Classically derived trajectory-based profiles are subject to two approximate desymmetrization procedures so that resulting profiles conform to the quantum principle of detailed balance. The simulated profiles are compared to laboratory measurements and employed for modeling Titan’s spectra in the 50-500 cm$^{-1}$ range. Based on the desymmetrized simulated profiles, a new semi-empirical model for CH$_4-$N$_2$ CIA is proposed for modeling Titan’s infrared spectra. Synthetic spectra derived using this model yield an excellent agreement with the data recorded by the Composite Infrared Spectrometer (CIRS) aboard the Cassini spacecraft at low and high emission angles.

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A. Finenko, B. Bézard, I. Gordon, et. al.
Thu, 4 Nov 21
16/73

Comments: 18 pages, 11 figures, accepted for publication in ApJS . The semiempirical CH4-N2 profiles tabulated in the HITRAN CIA format are available on the ApJS website or upon reasonable request

Experimental and computational studies on the reactivity of methanimine radical cation (H$_2$CNH$^{+\cdot}$) and its isomer aminomethylene (HCNH$_2^{+\cdot}$) with C$_2$H$_2$ [CL]

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http://arxiv.org/abs/2111.01794


Experimental and theoretical studies are presented on the reactivity of the radical cation isomers methanimine and aminomethylene with ethyne. Selective isomer generation is performed via dissociative photoionization of suitable neutral precursors and via direct photoionization of methanimine. Reactive cross sections and product branching ratios are measured as a function of photon and collision energies. Results are discussed in light of ab initio calculations of reaction mechanisms. The major channels, for both isomers, are due to H atom elimination from covalently bound adducts to give [C3NH4]+. Theoretical calculations show that while for the reaction of aminomethylene with acetylene any of the three lowest energy [C3NH4]+ isomers can form via barrierless and exothermic pathways, for the methanimine reagent the only barrierless pathway is the one leading to the production of protonated vinyl cyanide (CH2CHCNH+), a prototypical branched nitrile species that has been proposed as a likely intermediate in star forming regions and in the atmosphere of Titan. The astrochemical implications of the results are briefly addressed.

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V. Richardson, D. Ascenzi, D. Sundelin, et. al.
Thu, 4 Nov 21
60/73

Comments: 16 pages, 8 figures, 2 Tables. Supplementary material available at Publisher’s site

The reactivity of methanimine radical cation (H$_2$CNH$^{+\cdot}$) and its isomer aminomethylene (HCNH$_2^{+\cdot}$) with C$_2$H$_4$ [CL]

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http://arxiv.org/abs/2111.01703


Experimental and theoretical studies are presented on the reactivity of methanimine and aminomethylene cations with ethene. Selective isomer generation is performed via dissociative photoionization of suitable neutral precursors and reactive cross sections and branching ratios are measured as a function of photon and collision energies.

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D. Sundelin, D. Ascenzi, V. Richardson, et. al.
Wed, 3 Nov 21
49/106

Comments: 15 pages, 6 figures, 2 Tables

Computational investigation on the thermodynamics of H2CO + NH2 NH2CHO + H on interstellar water ice surfaces [CL]

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http://arxiv.org/abs/2111.00904


Formamide has a key role in prebiotic chemistry as it is the simplest molecule containing the four most important atoms from a biological point of view: hydrogen, carbon, nitrogen and oxygen. Due to its importance, the formation of this molecule has been studied and different pathways have been considered both in gas-phase and on ices of dust grains since it was first detected. In the present work, the thermodynamics of the formation route of formamide starting from NH2 and H2CO, a reaction channel proposed to occur in the gas phase, has been theoretically investigated in the scenario taking place on icy dust grains modelled by both a cluster and a periodic approach. Different DFT functionals have been employed to obtain accurate energy values for the mechanistic steps involved in the reaction.

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B. Martínez-Bachs and A. Rimola
Tue, 2 Nov 21
3/93

Comments: Proceedings of the 21st International Conference on Computational Science and Its Applications, ICCSA 2021

Origin of Chirality in the Molecules of Life [CL]

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http://arxiv.org/abs/2110.12232


Molecular chirality is inherent to biology and cellular chemistry. In this report, the origin of enantiomeric selectivity is analyzed from the viewpoint of the “RNA World” model, based on the autocatalytic self-replication of glyceraldehyde as a precursor for simple sugars, and in particular ribose, as promoted by the formose reaction. Autocatalytic coupling of formaldehyde and glycolaldehyde produces glyceraldehyde, which contains a chiral carbon center that is carried through in formation of the ribose ring. The parity non-conserving weak interaction is the only inherently handed property in nature and is herein shown to be sufficient to differentiate between two enantiomeric forms in an autocatalytic reaction performed over geologically relevant time scales, but only in the presence of a catalytic metal ion such as divalent calcium or higher Z alkaline earth elements. This work details calculations of the magnitude of the effect, the impact of various geologically-available metal ions, and the influence on evolution and dominance of chirality in the molecules of life.

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J. Cowan and R. Furnstahl
Tue, 26 Oct 21
102/109

Comments: 18 pages, 1 figures; supplementary material included with 9 pages, 4 figures

Alternation of Singlet and Triplet States in Carbon-Based Chain Molecules and Its Astrochemical Implications. Results of an Extensive Theoretical Study [CL]

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http://arxiv.org/abs/2110.11071


A variety of homologous carbon chains (HCnH, HCnN, CnS, CnO, and OCnO) are found to exhibit an appealing even-odd effect. Chains containing a number of carbon atoms of a certain parity possess singlet ground states, while members of opposite parity have triplet ground states. From a general perspective, it is important that this even-odd effect confounds straightforward chemical intuition. Whether the most stable form is a triplet or a singlet is neither simply related to the fact that the species in question is a normal (closed-shell, nonradical) molecule nor a (di)radical or to the (e.g., cumulene-type) C-C bond succession across the chain. From a computational perspective, the present results are important also because they demonstrate that electron correlations in carbon-based chains are extremely strong. Whether the gold-standard CCSD(T) (coupled-cluster expansions with single and double excitations and triple excitations corrections) framework suffices to describe such strongly correlated systems remains an open question that calls for further clarification. Most importantly for astrochemistry, the present results may explain why certain members are not astronomically observed although larger members of the same homologous series are detected; the missing species are exactly those for which the present calculations predict triplet ground states.

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I. Baldea
Fri, 22 Oct 21
22/133

Comments: The present posting includes important corrections of the values presented in the supporting information of the published paper

IRMPD spectroscopy of a PAH cation using FELICE: The infrared spectrum and photodissociation of dibenzo[a,l]pyrene [CL]

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http://arxiv.org/abs/2110.09249


We present the experimental InfraRed Multiple Photon Dissociation (IRMPD) spectrum and fragmentation mass spectrum of the irregular, cationic PAH dibenzo[a,l]pyrene (C${24}$H${14}^+$) in the 6-40 $\mu$m / 250-1650 cm$^{-1}$ range. The use of the the Free-Electron Laser for IntraCavity Experiments (FELICE) enabled us to record its Far-InfraRed (FIR) spectrum for the first time. We aim to understand how irregularity affects the infrared spectrum and fragmentation chemistry of PAHs. Dibenzo[a,l]pyrene is an asymmetric, non-planar molecule, for which all vibrational modes are in principle IR-active. Calculated harmonic Density Function Theory (DFT) and anharmonic Density Functional based Tight Binding Molecular Dynamics (DFTB-MD) spectra show a large wealth of bands, which match the experiment well, but with a few differences. The periphery of the molecule contains several edge geometries, but out of all possible modes in the 11-14 $\mu$m out-of-plane C-H bending region, only one band at 13.5 $\mu$m is prominent. This fact and the richness of the C-C stretching range make irregular PAHs a possible contributor to D-class interstellar spectra. The fragmentation mass spectra reveal facile 2H-loss and no [2C, 2H]-loss, which is attributed to the sterically hindered, non-planar cove region, which could protect irregular PAHs from radiation damage.

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S. Wiersma, A. Candian, M. Rapacioli, et. al.
Tue, 19 Oct 21
17/98

Comments: Accepted for publication in The Journal of Molecular Spectroscopy

Diastereoselective Formation of trans-HC(O)SH Through Hydrogenation of OCS on Interstellar Dust Grains [GA]

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http://arxiv.org/abs/2110.02778


With the presence of evermore complex S-bearing molecules being detected lately, studies on their chemical formation routes need to keep up the pace to rationalize observations, suggest new candidates for detection, and provide input for chemical evolution models. In this paper, we theoretically characterize the hydrogenation channels of OCS on top of amorphous solid water as an interstellar dust grain analog in molecular clouds. Our results show that the significant reaction outcome is trans-HC(O)SH, a recently detected prebiotic molecule toward G+0.693. The reaction is diastereoselective, explaining the seemingly absence of the cis isomer in the astronomical observations. We found that the reaction proceeds through a highly localized radical intermediate (cis-OCSH), which could be essential in the formation of other sulfur-bearing complex organic molecules due to its slow isomerization dynamics on top of amorphous solid water.

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G. Molpeceres, J. Concepción and I. Serra
Thu, 7 Oct 21
33/51

Comments: Accepted in ApJ

On the stability of satellites at unstable libration points of sun-planet-moon systems [EPA]

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http://arxiv.org/abs/2109.12612


The five libration points of a sun-planet system are stable or unstable fixed positions at which satellites or asteroids can remain fixed relative to the two orbiting bodies. A moon orbiting around the planet causes a time-dependent perturbation on the system. Here, we address the sense in which invariant structure remains. We employ a transition state theory developed previously for periodically driven systems with a rank-1 saddle in the context of chemical reactions. We find that a satellite can be parked on a so-called time-periodic transition state trajectory — which is an orbit restricted to the vicinity of the libration point L2 for infinitely long time — and investigate the stability properties of that orbit.

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J. Reiff, J. Zatsch, J. Main, et. al.
Tue, 28 Sep 21
19/89

Comments: Main article has 15 pages, 6 figures. arXiv admin note: text overlap with arXiv:2011.04029

Vibrational and Rotational Spectral Data for Possible Interstellar Detection of AlH$_3$OH$_2$, SiH$_3$OH, and SiH$_3$NH$_2$ [IMA]

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http://arxiv.org/abs/2109.11605


This work provides the first full set of vibrational and rotational spectral data needed to aid in the detection of AlH$_3$OH$_2$, SiH$_3$OH, and SiH$_3$NH$_2$ in astrophysical or simulated laboratory environments through the use of quantum chemical computations at the CCSD(T)-F12b level of theory employing quartic force fields for the three molecules of interest. Previous work has shown that SiH$_3$OH and SiH$_3$NH$_2$ contain some of the strongest bonds of the most abundant elements in space. AlH$_3$OH$_2$ also contains highly abundant atoms and represents an intermediate along the reaction pathway from H$_2$O and AlH$_3$ to AlH$_2$OH. All three of these molecules are also polar with AlH$_3$OH$_2$ having the largest dipole of 4.58 D and the other two having dipole moments in the 1.10-1.30 D range, large enough to allow for the detection of these molecules in space through rotational spectroscopy. The molecules also have substantial infrared intensities with many of the frequencies being over 90 km mol$^{-1}$ and falling within the currently uncertain 12-17 $\mu$m region of the spectrum. The most intense frequency for AlH$_3$OH$_2$ is $\nu_9$ which has an intensity of 412 km mol$^{-1}$ at 777.0 cm$^{-1}$ (12.87 $\mu$m). SiH$-3$OH has an intensity of 183 km mol$^{-1}$ at 1007.8 cm$^{-1}$ (9.92 $\mu$m) for $\nu_5$, and SiH$_3$NH$_2$ has an intensity of 215 km mol$^{-1}$ at 1000.0 cm$^{-1}$ (10.00 $\mu$m) for $\nu_7$.

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A. Watrous, B. Westbrook, M. Davis, et. al.
Mon, 27 Sep 21
20/68

Comments: 7 pages, 2 figures, accepted in MNRAS

Abiotic molecular oxygen production — ionic pathway from sulphur dioxide [EPA]

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http://arxiv.org/abs/2108.12672


Molecular oxygen, O$_2$, is vital to life on Earth and possibly on other planets. Although the biogenic processes leading to its accumulation in Earth’s atmosphere are well understood, its abiotic origin is still not fully established. Here, we report combined experimental and theoretical evidence for electronic-state-selective production of O$_2$ from SO$_2$, a major chemical constituent of many planetary atmospheres and one which played an important part on Earth in the Great Oxidation event. The O$_2$ production involves dissociative double ionisation of SO$_2$ leading to efficient formation of the O$_2^+$ ion which can be converted to abiotic O$_2$ by electron neutralisation. We suggest that this formation process may contribute significantly to the abundance of O$_2$ and related ions in planetary atmospheres, especially in those where CO$_2$, which can lead to O$_2$ production by different mechanisms, is not the dominant component.

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M. Wallner, M. Jarraya, S. Yaghlane, et. al.
Tue, 31 Aug 21
58/73

Comments: N/A

Formation of phosphorus monoxide (PO) in the interstellar medium: insights from quantum-chemical and kinetic calculations [GA]

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http://arxiv.org/abs/2108.08530


In recent years, phosphorus monoxide (PO) — an important molecule for prebiotic chemistry — has been detected in star-forming regions and in the comet 67P/Churyumov-Gerasimenko. These studies have revealed that, in the interstellar medium, PO is systematically the most abundant P-bearing species, with abundances that are $\sim$1-3 times greater than those derived for phosphorus nitride (PN), the second most abundant P-containing molecule. The reason why PO is more abundant than PN remains still unclear. Experimental studies with phosphorus in the gas phase are not available, probably because of the difficulties in dealing with its compounds. Therefore, the reactivity of atomic phosphorus needs to be investigated using reliable computational tools. To this end, state-of-the-art quantum-chemical computations have been employed to evaluate accurate reaction rates and branching ratios for the P + OH $\rightarrow$ PO + H and P + H$_2$O $\rightarrow$ PO + H$_2$ reactions in the framework of a master equation approach based on ab-initio transition state theory. The hypothesis that OH and H${_2}$O can be potential oxidizing agents of atomic phosphorus is based on the ubiquitous presence of H${_2}$O in the ISM. Its destruction then produces OH, which is another very abundant species. While the reaction of atomic phosphorus in its gound state with water is not a relevant source of PO because of emerged energy barriers, the P + OH reaction represents an important formation route of PO in the interstellar medium. Our kinetic results show that this reaction follow an Arrhenius behavior, and thus its rate coefficients alpha=2.28$\times$10$^{-10}$ cm${^3}$ molecule$^{-1}$ s$^{-1}$, beta=0.16 and gamma=0.37 K increase by increasing the temperature.

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J. Concepción, C. Puzzarini, V. Barone, et. al.
Fri, 20 Aug 21
48/59

Comments: 21 pages, 5 figures

Machine Learning of Interstellar Chemical Inventories [GA]

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http://arxiv.org/abs/2107.14610


The characterization of interstellar chemical inventories provides valuable insight into the chemical and physical processes in astrophysical sources. The discovery of new interstellar molecules becomes increasingly difficult as the number of viable species grows combinatorially, even when considering only the most thermodynamically stable. In this work, we present a novel approach for understanding and modeling interstellar chemical inventories by combining methodologies from cheminformatics and machine learning. Using multidimensional vector representations of molecules obtained through unsupervised machine learning, we show that identification of candidates for astrochemical study can be achieved through quantitative measures of chemical similarity in this vector space, highlighting molecules that are most similar to those already known in the interstellar medium. Furthermore, we show that simple, supervised learning regressors are capable of reproducing the abundances of entire chemical inventories, and predict the abundance of not yet seen molecules. As a proof-of-concept, we have developed and applied this discovery pipeline to the chemical inventory of a well-known dark molecular cloud, the Taurus Molecular Cloud 1 (TMC-1); one of the most chemically rich regions of space known to date. In this paper, we discuss the implications and new insights machine learning explorations of chemical space can provide in astrochemistry.

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K. Lee, J. Patterson, A. Burkhardt, et. al.
Mon, 2 Aug 21
3/82

Comments: 20 pages; 8 figures, 2 tables in the main text. 6 figures, 2 tables in the appendix. Accepted for publication in The Astrophysical Journal Letters. Molecule recommendations for TMC-1 can be found in the Zenodo repository: this https URL

Detectable Abundance of Cyanoacetylene (HC$_3$N) Predicted on Reduced Nitrogen-Rich Super-Earth Atmospheres [EPA]

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http://arxiv.org/abs/2107.13097


We predict that cyanoacetylene (HC$_3$N) is produced photochemically in the atmosphere of GJ 1132 b in abundances detectable by the James Webb Space Telescope (JWST), assuming that the atmosphere is as described by Swain et al. (2021). First, we construct line list and cross-sections for HC$_3$N. Then we apply these cross-sections and the model atmosphere of Swain et al. (2021) to a radiative transfer model in order to simulate the transmission spectrum of GJ 1132 b as it would be seen by JWST, accounting for the uncertainty in the retrieved abundances. We predict that cyanoacetylene features at various wavelengths, with a clear lone feature at 4.5 $\mu$m, observable by JWST after four transits. This feature persists within the $1-\sigma$ uncertainty of the retrieved abundances of HCN and CH$_4$.

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P. Rimmer, L. Majumdar, A. Priyadarshi, et. al.
Thu, 29 Jul 21
53/59

Comments: 10 pages, 5 figures, submitted to ApJL, comments welcome

Depolarization of MgH Solar Lines by Collisions with Hydrogen Atoms [SSA]

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http://arxiv.org/abs/2107.11909


Interpretations of the very rich second solar spectrum of the MgH molecule face serious problems owing to the complete lack of any information about rates of collisions between the MgH and hydrogen atoms. This work seeks to begin the process of filling this lacuna by providing, for the first time, quantum excitation, depolarization, and polarization transfer collisional rates of the MgH ground state $X^2\Sigma$. To achieve the goals of this work, potential energy surfaces are calculated and then are included in the Schr\”odinger equation to obtain the probabilities of collisions and, thus, all collisional rates. Our rates are obtained for temperatures ranging from $T !!=$2000 K to $T !!=$15,000 K. Sophisticated genetic programming methods are adopted in order to fit all depolarization rates with useful analytical functions of two variables: the total molecular angular momentum and temperatures. We study the solar implications of our results, and we find that the $X^2\Sigma$ state of MgH is partially depolarized by isotropic collisions with neutral hydrogen in its ground state $^2S$. Our findings show the limits of applicability of the widely used approximation in which the lower-level polarization is neglected.

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S. Qutub, Y. Kalugina and M. Derouich
Tue, 27 Jul 21
68/97

Comments: Published in The Astrophysical Journal

X-ray induced desorption and photochemistry in CO ice [CL]

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http://arxiv.org/abs/2107.10503


We report an investigation of X-ray induced desorption of neutrals, cations and anions from CO ice. The desorption of neutral CO, by far the most abundant, is quantified and discussed within the context of its application to astrochemistry. The desorption of many different cations, including large cations up to the mass limit of the spectrometer, are observed. In contrast, the only desorbing anions detected are O$^-$ and C$^-$. The desorption mechanisms of all these species are discussed with the aid of their photodesorption spectrum. The evolution of the X-ray absorption spectrum shows significant chemical modifications of the ice upon irradiation, which along with the desorption of large cations gives a new insight into X-ray induced photochemistry in CO ice.

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{. Dupuy, M. Bertin, G. Féraud, et. al.
Fri, 23 Jul 21
58/63

Comments: Accepted in PCCP

The vibrational properties of benzene on an ordered water ice surface [CL]

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http://arxiv.org/abs/2107.08826


We present a hybrid CCSD(T)+PBE-D3 approach to calculating the vibrational signatures for gas phase benzene and benzene adsorbed on an ordered water-ice surface. We compare the results of our method against experimentally recorded spectra and calculations performed using PBE-D3-only approaches (harmonic and anharmonic). Calculations use a proton ordered XIh water-ice surface consisting of 288 water molecules, and results are compared against experimental spectra recorded for an ASW ice surface. We show the importance of including a water ice surface into spectroscopic calculations, owing to the resulting differences in vibrational modes, frequencies and intensities of transitions seen in the IR spectrum. The overall intensity pattern shifts from a dominating $\nu_{11}$ band in the gas-phase to several high-intensity carriers for an IR spectrum of adsorbed benzene. When used for adsorbed benzene, the hybrid approach presented here achieves an RMSD for IR active modes of 21~cm$^{-1}$, compared to 72~cm$^{-1}$ and 49~cm$^{-1}$ for the anharmonic and harmonic PBE-D3 approaches, respectively. Our hybrid model for gaseous benzene also achieves the best results when compared to experiment, with an RMSD for IR active modes of 24~cm$^{-1}$, compared to 55~cm$^{-1}$ and 31~cm$^{-1}$ for the anharmonic and harmonic PBE-D3 approaches, respectively. To facilitate assignment, we generate and provide a correspondence graph between the normal modes of the gaseous and adsorbed benzene molecules. Finally, we calculate the frequency shifts, $\Delta\nu$, of adsorbed benzene relative to its gas phase to highlight the effects of surface interactions on vibrational bands and evaluate the suitability of our chosen dispersion-corrected density functional theory.

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V. Clark and D. Benoit
Wed, 21 Jul 21
77/83

Comments: N/A

Quantum nature of molecular vibrational quenching: Water – molecular hydrogen collisions [CL]

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http://arxiv.org/abs/2107.08044


Rates of conversions of molecular internal energy to and from kinetic energy by means of molecular collision allows to compute collisional line shapes and transport properties of gases. Knowledge of ro-vibrational quenching rates is necessary to connect spectral observations to physical properties of warm astrophysical gasses, including exo-atmospheres. For a system of paramount importance in this context, the vibrational bending mode quenching of H2O by H2, we show here that exchange of vibrational to rotational and kinetic energy remains a quantum process, despite the large numbers of quantum levels involved and the large vibrational energy transfer. The excitation of the quantized rotor of the projectile is by far the most effective ro-vibrational quenching path of water. To do so, we use a fully quantum first principle computation, potential and dynamics, converging it at all stages, in a full coupled channel formalisms. We present here rates for the quenching of the first bendingmode of ortho-H2O by ortho H2, up to 500K, in a fully converged coupled channels formalism.

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L. Wiesenfeld
Mon, 19 Jul 21
28/70

Comments: 17 pages, 5 figures

A new equation of state for dense hydrogen-helium mixtures II: taking into account hydrogen-helium interactions [SSA]

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http://arxiv.org/abs/2107.04434


In a recent paper (Chabrier et al. 2019), we have derived a new equation of state (EOS) for dense hydrogen/helium mixtures which covers the temperature-density domain from solar-type stars to brown dwarfs and gaseous planets. This EOS is based on the so-called additive volume law and thus does not take into account the interactions between the hydrogen and helium species. In the present paper, we go beyond these calculations by taking into account H/He interactions, derived from quantum molecular dynamics simulations. These interactions, which eventually lead to H/He phase separation, become important at low temperature and high density, in the domain of brown dwarfs and giant planets. The tables of this new EOS are made publicly available.

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G. Chabrier and F. Debras
Mon, 12 Jul 21
5/49

Comments: To be published in The Astrophysical Journal

Carbon dioxide clathrate hydrate formation at low temperature. Diffusion-limited kinetics growth as monitored by FTIR [CL]

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http://arxiv.org/abs/2107.01377


The formation and presence of clathrate hydrates could influence the composition and stability of planetary ices and comets; they are at the heart of the development of numerous complex planetary models, all of which include the necessary condition imposed by their stability curves, some of which include the cage occupancy or host-guest content and the hydration number, but fewer take into account the kinetics aspects. We measure the temperature-dependent-diffusion-controlled formation of the carbon dioxide clathrate hydrate in the 155-210~K range in order to establish the clathrate formation kinetics at low temperature. We exposed thin water ice films of a few microns in thickness deposited in a dedicated infrared transmitting closed cell to gaseous carbon dioxide maintained at a pressure of a few times the pressure at which carbon dioxide clathrate hydrate is thermodynamically stable. The time dependence of the clathrate formation was monitored with the recording of specific infrared vibrational modes of CO2 with a Fourier Transform InfraRed (FTIR) spectrometer. These experiments clearly show a two-step clathrate formation, particularly at low temperature, within a relatively simple geometric configuration. We satisfactorily applied a model combining surface clathration followed by a bulk diffusion-relaxation growth process to the experiments and derived the temperature-dependent-diffusion coefficient for the bulk spreading of clathrate. The derived apparent activation energy corresponding to this temperature-dependent-diffusion coefficient in the considered temperature range is E_a = 24.7 +/- 9.7 kJ/mol. The kinetics parameters favour a possible carbon dioxide clathrate hydrate nucleation mainly in planets or satellites.

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E. Dartois and F. Langlet
Tue, 6 Jul 21
54/74

Comments: N/A

Molecular Chemistry for Dark Matter [CEA]

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http://arxiv.org/abs/2106.13245


Molecular cooling is essential for studying the formation of sub-structure of dissipative dark-matter halos that may host compact objects such as black holes. Here, we analyze the reaction rates relevant for the formation, dissociation, and transition of hydrogenic molecules while allowing for different values of the physical parameters: the coupling constant, the proton mass, and the electron mass. For all cases, we re-scale the reaction rates for the standard molecular hydrogen, so our results are valid as long as the dark matter is weakly coupled and one of the fermions is much heavier than the other. These results will allow a robust numerical treatment of cosmic structure, in particular for mini-halos for which molecular cooling is important, in a dissipative dark matter scenario.

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M. Ryan, J. Gurian, S. Shandera, et. al.
Mon, 28 Jun 21
41/51

Comments: 26 pages, 5 figures

Vibrational effects in the quantum dynamics of the H + D_2^+ charge transfer reaction [CL]

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http://arxiv.org/abs/2106.13190


The H + D_2^+(v=0,1 and 2) charge transfer reaction is studied using an accurate wave packet method, using recently proposed coupled diabatic potential energy surfaces. The state-to-state cross section is obtained for three different channels: non-reactive charge transfer, reactive charge transfer, and exchange reaction. The three processes proceed via the electronic transition from the first excited to the ground electronic state. The cross section for the three processes increases with the initial vibrational excitation. The non-reactive charge transfer process is the dominant channel, whose branching ratio increases with collision energy, and it compares well with experimental measurements at collision energies around 0.5 eV. For lower energies the experimental cross section is considerably higher, suggesting that it corresponds to higher vibrational excitation of D_2^+(v) reactants. Further experimental studies of this reaction and isotopic variants are needed, where conditions are controlled to obtain a better analysis of the vibrational effects of the D_2^+ reagents.

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O. Roncero, V. Andrianarijaona, A. Aguado, et. al.
Fri, 25 Jun 21
8/62

Comments: 15 pages, 7 figures

A Large-scale Approach to Modelling Molecular Biosignatures: The Diatomics [CL]

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http://arxiv.org/abs/2106.07647


This work presents the first steps to modelling synthetic rovibrational spectra for all molecules of astrophysical interest using the new code Prometheus. The goal is to create a new comprehensive source of first-principles molecular spectra, thus bridging the gap for missing data to help drive future high-resolution studies. Our primary application domain is on molecules identified as signatures of life in planetary atmospheres (biosignatures). As a starting point, in this work we evaluate the accuracy of our method by studying the diatomics molecules H$_2$, O$_2$, N$_2$ and CO, all of which have well-known spectra. Prometheus uses the Transition-Optimised Shifted Hermite (TOSH) theory to account for anharmonicity for the fundamental $\nu=0 \rightarrow \nu=1$ band, along with thermal profile modeling for the rotational transitions. We present a novel new application of the TOSH theory with regards to rotational constants. Our results show that this method can achieve results that are a better approximation than the ones produced through the basic harmonic method. We discuss the current limitations of our method. In particular, we compare our results with high-resolution HITRAN spectral data. We find that modelling accuracy tends to diminish for rovibrational transition away from the band origin, thus highlighting the need for the theory to be further adapted.

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T. Cross, D. Benoit, M. Pignatari, et. al.
Wed, 16 Jun 21
51/57

Comments: N/A

Visible-Light Photoionization of Aromatic Molecules in Water-Ice: Organic Chemistry across the Universe with Less Energy [GA]

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http://arxiv.org/abs/2106.04623


Ionization of gas-phase organic molecules such as polycyclic aromatic hydrocarbons (PAHs) requires vacuum ultraviolet photons at wavelengths shorter than 200 nm (~6-9 eV). We present here for the first time that visible photons – accessible through sunlight – can cause photoionization of trapped PAHs in cryogenic water-ice, accounting for 4.4 eV less ionization energy than in the gas phase. This finding opens up new reaction pathways involving low-energy ionization in many environments where water and organic matter coexist. This include the interstellar medium, molecular clouds, protoplanetary disks, and planetary surfaces and atmospheres (including Earth).

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A. Lignell, L. Tanalenda-Ossorio and M. Gudipati
Thu, 10 Jun 21
29/77

Comments: Accepted to Chem. Phys. Lett., 34 pages, 4 figures, 8 supplementary figures

Full Spectroscopic Model and Trihybrid Experimental-Perturbative-Variational Line List for CN [CL]

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http://arxiv.org/abs/2105.13917


Accurate line lists are important for the description of the spectroscopic nature of small molecules. While a line list for CN (an important molecule for chemistry and astrophysics) exists, no underlying energy spectroscopic model has been published, which is required to consider the sensitivity of transitions to a variation of the proton-to-electron mass ratio.
Here we have developed a Duo energy spectroscopic model as well as a novel hybrid style line list for CN and its isotopologues, combining energy levels that are derived experimentally (Marvel), using the traditional/perturbative approach (Mollist), and the variational approach (from a Duo spectroscopic model using standard ExoMol methodology). The final Trihybrid ExoMol-style line list for 12C14N consists of 28,004 energy levels (6,864 experimental, 1,574 perturbative, the rest variational) and 2,285,103 transitions up to 60,000 cm-1 between the three lowest electronic states (X2Sigma+, A2Pi and B2Sigma+). The spectroscopic model created is used to evaluate CN as a molecular probe to constrain the variation of the proton-to-electron mass ratio; no overly promising sensitive transitions for extragalactic study were identified.

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A. Syme and L. McKemmish
Mon, 31 May 21
64/72

Comments: Accepted in Monthly Notices of the Royal Astronomical Society. 13 pages, 11 figures

Anharmonic Vibrational Spectrum and Experimental Matrix Isolation Study of Thioformic Acid Conformers — Potential Candidates for Molecular Cloud and Solar System Observations? [GA]

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http://arxiv.org/abs/2105.11963


Thioformic acid (TFA) is the sulfur analog of formic acid, the simplest organic acid. It has three analogues HCOSH, HCSOH, and HCSSH, each of them having two rotational isomeric (rotameric) forms: trans and cis where the trans form is energetically more stable. In this article, we study computational energetics and anharmonic vibrational spectrum of TFA including overtone and combination vibrations. We also studied experimental photoisomerization and photodecomposition channels of HCOSH molecules with different wavelengths. We suggest that TFA is a potential sulfur containing candidate molecule for interstellar and planetary observations and discuss these in a light of different radiation environments in space. More generally, we discuss that infrared radiation driven photo-isomerization reactions may be a common phenomenon in such environments and can affect the chemical reaction pathways of organic and other interstellar molecules.

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A. Lignell, I. Osadchuk, M. Rasanen, et. al.
Wed, 26 May 21
31/66

Comments: Accepted to ApJ, 21 pages, 4 figures

Computational Infrared Spectroscopy of 958 Phosphorus-bearing Molecules [EPA]

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http://arxiv.org/abs/2105.08897


Phosphine is now well established as a biosignature, which has risen to prominence with its recent tentative detection on Venus. To follow up this discovery and related future exoplanet biosignature detections, it is important to spectroscopically detect the presence of phosphorus-bearing atmospheric molecules that could be involved in the chemical networks producing, destroying or reacting with phosphine. We start by enumerating phosphorus-bearing molecules (P-molecules) that could potentially be detected spectroscopically in planetary atmospheres and collecting all available spectral data. Gaseous P-molecules are rare, with speciation information scarce. Very few molecules have high accuracy spectral data from experiment or theory; instead, the best available data is from the RASCALL approach and obtained using functional group theory. Here, we present a high-throughput approach utilising established computational quantum chemistry methods (CQC) to produce a database of approximate infrared spectra for 958 P-molecules. These data are of interest for astronomy and astrochemistry (importantly identifying potential ambiguities in molecular assignments), improving RASCALL’s underlying data, big data spectral analysis and future machine learning applications. However, this data will probably not be sufficiently accurate for secure experimental detections of specific molecules within complex gaseous mixtures in laboratory or astronomy settings.

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J. Trujilo, A. Syme, K. Rowell, et. al.
Thu, 20 May 21
41/56

Comments: 36 pages, 10 figures

Mass-independent analysis of the stable isotopologues of gas-phase titanium monoxide — TiO [CL]

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http://arxiv.org/abs/2105.09036


More than 130 pure rotational transitions of $^{46}$TiO, $^{47}$TiO, $^{48}$TiO, $^{49}$TiO, $^{50}$TiO, and $^{48}$Ti$^{18}$O are recorded using a high-resolution mm-wave supersonic jet spectrometer in combination with a laser ablation source. For the first time a mass-independent Dunham-like analysis is performed encompassing rare titanium monoxide isotopologues, and are compared to results from high-accuracy quantum-chemical calculations. The obtained parametrization reveals for titanium monoxide effects due to deviations from the Born-Oppenheimer approximation. Additionally, the dominant titanium properties enable an insight into the electronic structure of TiO by analyzing its hyperfine interactions. Further, based on the mass-independent analysis, the frequency positions of the pure rotational transitions of the short lived rare isotopologue $^{44}$TiO are predicted with high accuracy, i.e., on a sub-MHz uncertainty level. This allows for dedicated radio-astronomical searches of this species in core-collapse environments of supernovae.

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A. Breier, B. Waßmuth, G. Fuchs, et. al.
Thu, 20 May 21
53/56

Comments: 29 pages, 3 figures

Study of Fischer-Tropsch Type reactions on chondritic meteorites [EPA]

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http://arxiv.org/abs/2105.08498


How simple organic matter appeared on Earth and the processes by which it transformed into more evolved organic compounds, which ultimately led to the emergence of life, is still an open topic. Different scenarios have been proposed, the main one assumes that simple organic compounds were synthesized, either in the gas phase or on the surfaces of dust grains, during the process of star formation, and were incorporated into larger bodies in the protoplanetary disk. Transformation of these simple organic compounds in more complex forms is still a matter of debate. Recent discoveries point out to catalytic properties of dust grains present in the early stellar envelope, which can nowadays be found in the form of chondrites. The huge infall of chondritic meteorites during the early periods of Earth suggests that the same reactions could have taken place in certain environments of the Earth surface, with conditions more favorable for organic synthesis. This work attempts the synthesis of simple organic molecules, such as hydrocarbons and alcohols, via Fischer-Tropsch Type reactions supported by different chondritic materials under early-Earth conditions, to investigate if organic synthesis can likely occur in this environment and which are the differences in selectivity when using different types of chondrites. Fischer-Tropsch-type reactions are investigated from mixtures of CO and H2 at 1 atm of pressure on the surfaces of different chondritic samples. The different products obtained are analyzed in situ by gas chromatography. Different Fischer-Tropsch reaction products are obtained in quantitative amounts. The formation of alkanes and alkenes being the main processes. Formation of alcohols also takes place in a smaller amount. Other secondary products were obtained in a qualitative way.

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V. Cabedo, J. Llorca, J. Trigo-Rodríguez, et. al.
Wed, 19 May 21
15/64

Comments: Accepted for publication in Astronomy and Astrophysics

Detection of Interstellar H$_2$CCCHC$_3$N [GA]

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http://arxiv.org/abs/2105.03347


The chemical pathways linking the small organic molecules commonly observed in molecular clouds to the large, complex, polycyclic species long-suspected to be carriers of the ubiquitous unidentified infrared emission bands remain unclear. To investigate whether the formation of mono- and poly-cyclic molecules observed in cold cores could form via the bottom-up reaction of ubiquitous carbon-chain species with, e.g. atomic hydrogen, a search is made for possible intermediates in data taken as part of the GOTHAM (GBT Observations of TMC-1 Hunting for Aromatic Molecules) project. Markov-Chain Monte Carlo (MCMC) Source Models were run to obtain column densities and excitation temperatures. Astrochemical models were run to examine possible formation routes, including a novel grain-surface pathway involving the hydrogenation of C$_6$N and HC$_6$N, as well as purely gas-phase reactions between C$_3$N and both propyne (CH$_3$CCH) and allene (CH$_2$CCH$_2$), as well as via the reaction CN + H$_2$CCCHCCH. We report the first detection of cyanoacetyleneallene (H$_2$CCCHC$_3$N) in space toward the TMC-1 cold cloud using the Robert C. Byrd 100 m Green Bank Telescope (GBT). Cyanoacetyleneallene may represent an intermediate between less-saturated carbon-chains, such as the cyanopolyynes, that are characteristic of cold cores and the more recently-discovered cyclic species like cyanocyclopentadiene. Results from our models show that the gas-phase allene-based formation route in particular produces abundances of H$_2$CCCHC$_3$N that match the column density of $2\times10^{11}$ cm$^{-2}$ obtained from the MCMC Source Model, and that the grain-surface route yields large abundances on ices that could potentially be important as precursors for cyclic molecules.

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C. Shingledecker, K. Lee, J. Wandishin, et. al.
Mon, 10 May 21
60/60

Comments: Accepted in A&A Letters

Physics and Chemistry on the Surface of Cosmic Dust Grains: A Laboratory View [GA]

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http://arxiv.org/abs/2105.01387


Dust grains play a central role in the physics and chemistry of cosmic environments. They influence the optical and thermal properties of the medium due to their interaction with stellar radiation; provide surfaces for the chemical reactions that are responsible for the synthesis of a significant fraction of key astronomical molecules; and they are building blocks of pebbles, comets, asteroids, planetesimals, and planets. In this paper, we review experimental studies of physical and chemical processes, such as adsorption, desorption, diffusion, and reactions forming molecules, on the surface of reliable cosmic dust grain analogues as related to processes in diffuse, translucent, and dense interstellar clouds, protostellar envelopes, planet-forming disks, and planetary atmospheres. The information that such experiments reveal should be flexible enough to be used in many different environments. In addition, we provide a forward look discussing new ideas, experimental approaches, and research directions.

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A. Potapov and M. McCoustra
Wed, 5 May 21
57/61

Comments: Accepted for publication in International Reviews in Physical Chemistry

Millimeter-wave spectroscopy of the $^{13}$CH$_3$OD isotopic species of methyl alcohol [IMA]

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http://arxiv.org/abs/2104.14340


The dramatic increase in sensitivity, spectral coverage and resolution of radio astronomical facilities in recent years has opened new possibilities for observation of chemical differentiation and isotopic fractionation in protostellar sources to shed light on their spatial and temporal evolution. In warm interstellar environments, methanol is an abundant species, hence spectral data for its isotopic forms are of special interest. In the present work, the millimeter-wave spectrum of the $^{13}$CH$3$OD isotopologue has been investigated over the region from 150$-$510 GHz to provide a set of transition frequencies for potential astronomical application. The focus is on two types of prominent $^{13}$CH$_3$OD spectral groupings, namely the $a$-type $^qR$-branch multiplets and the $b$-type $Q$-branches. Line positions are reported for the $^qR(J)$ clusters for $J = 3$ to 10 for the $v{\rm t} = 0$ and 1 torsional states, and for a number of $v_{\rm t} = 0$ and 1 $^rQ(J)$ or $^pQ(J)$ line series up to $J = 25$. The frequencies have been fitted to a multi-parameter torsion-rotation Hamiltonian, and upper level excitation energies have been calculated from the resulting molecular constants.

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L. Xu, R. Lees, O. Zakharenko, et. al.
Fri, 30 Apr 21
56/59

Comments: 25 pages, 8 pages text and references