ExoMol molecular line lists — XLII: Rovibronic molecular line list for the low-lying states of NO [EPA]

http://arxiv.org/abs/2104.10854


An accurate line list, called XABC, is computed for nitric oxide which covers its pure rotational, vibrational and rovibronic spectra. A mixture of empirical and theoretical electronic transition dipole moments are used for the final calculation of $^{14}\mathrm{N}^{16}\mathrm{O}$ rovibronic $\mathrm{A}\,^2\Sigma^+$ — $\mathrm{X}\,^2\Pi$, $\mathrm{B}\,^2\Pi$ — $\mathrm{X}^2\Pi$ and $\mathrm{C}\,^2\Pi$ — $\mathrm{X}\,^2\Pi$ which correspond to the $\gamma$, $\beta$ and $\delta$ band systems, respectively, as well as minor improvements to transitions within the $\mathrm{X}\,^2\Pi$ ground state. The work is a major update of the ExoMol NOname line list. It provides a high-accuracy NO ultraviolet line list covering the complicated regions where the $\mathrm{B}\,^2\Pi$-$\mathrm{C}\,^2\Pi$ states interact. XABC provides comprehensive data for the lowest four doublet states of NO in the region of $\lambda > 160 ~ \mathrm{nm}$ ($\tilde{\nu} < 63~000~\mathrm{cm}^{-1}$) for the analysis of atmospheric NO on Earth, Venus or Mars, other astronomical observations and applications. The data is available via this http URL.

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Q. Qu, S. Yurchenko and J. Tennyson
Fri, 23 Apr 2021
23/48

Comments: 13 pages, 14 figures, 2 tables

Ammonia snow-lines and ammonium salts desorption [EPA]

http://arxiv.org/abs/2104.10464


Context. The nitrogen reservoir in planetary systems is a long standing problem. Part of the N-bearing molecules is probably incorporated into the ice bulk during the cold phases of the stellar evolution, and may be gradually released into the gas phase when the ice is heated, such as in active comets. The chemical nature of the N-reservoir should greatly influence how, when and in what form N returns to the gas phase, or is incorporated into the refractory material forming planetary bodies.
Aims. We present the study the thermal desorption of two ammonium salts: ammonium formate and ammonium acetate from a gold surface and from a water ice substrate.
Methods. Temperature-programmed desorption experiments and Fourier transform infrared reflection spectroscopy were conducted to investigate the desorption behavior of ammonium salts.
Results. Ammonium salts are semi-volatile species releasing neutral species as major components upon desorption, that is ammonia and the corresponding organic acid (HCOOH and CH3COOH), at temperatures higher than the temperature of thermal desorption of water ice. Their desorption follows a first-order Wigner-Polanyi law. We find the first order kinetic parameters A = 7.7 $\pm$ 0.6 $\times$ 10$^{15}$ s$^{-1}$ and E${bind}$ = 68.9 $\pm$ 0.1 kJ~mol$^{-1}$ for ammonium formate and A = 3.0 $\pm$ 0.4 $\times$ 10$^{20}$ s$^{-1}$ and E${bind}$ = 83.0 $\pm$ 0.2 kJ~mol$^{-1}$ for ammonium acetate. The presence of a water ice substrate does not influence the desorption kinetics. Ammonia molecules locked in salts desorb as neutral molecules at temperatures much higher than previously expected that are usually attributed to refractory materials.
Conclusions. Ammonia snow-line has a smaller radius than the water snow-line. As a result, the NH3/H2O ratio content in solar system bodies can be a hint as to where they formed and subsequently migrated.

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F. Kruczkiewicz, J. Vitorino, E. Congiu, et. al.
Thu, 22 Apr 2021
36/44

Comments: Accepted for publication in A&A, 10 pages, 7 figures

The origin of the E/Z isomer ratio of imines in the interstellar medium [CL]

http://arxiv.org/abs/2104.07913


Recent astronomical observations of both isomers E and Z of imines such as cyanomethanimine, ethanimine and 2-propyn-1-imine, have revealed that the abundances in the ISM of these isomers differ by factors of ~3-10. Several theories have been proposed to explain the observed behavior, but none of them successfully explains the [E]/[Z] ratios. In this work we present a detailed study of the kinetics of the one-step E-Z isomerization reactions of cyanomethanimine, ethanimine and 2-propyn-1-imine under interstellar conditions (in the 10-400 K temperature range). This reaction was previously thought to be non-viable in the ISM due to its associated high-energy barrier (about 13,000 K). In this Letter, we show that considering the multidimensional small curvature tunneling approximation, the tunneling effect enables the isomerization even at low temperatures. This is due to the fact that the representative tunneling energy lies in the vibrational ground state of the least stable isomer up to approximately 150 K, making the reaction constants of the isomerization from the least stable to the most stable isomer basically constant. The predicted [E]/[Z] ratios are almost the same as those reported from the astronomical observations for all imines observed. This study demonstrates that the [E]/[Z] ratio of imines in the ISM strongly depends on their relative stability.

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J. Concepción, I. Jiménez-Serra, J. Corchado, et. al.
Wed, 21 Apr 2021
5/72

Comments: 13 pages, 2 figures

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

http://arxiv.org/abs/2104.09434


The simultaneous detection of organic molecules of the form C$2$H${\text{n}}$O, such as ketene (CH$_2$CO), acetaldehyde (CH$_3$CHO), and ethanol (CH$_3$CH$_2$OH), toward early star-forming regions offers hints of shared chemical history. Several reaction routes have been proposed and experimentally verified under various interstellar conditions to explain the formation pathways involved. Most noticeably, the non-energetic processing of C$_2$H$_2$ ice with OH-radicals and H-atoms was shown to provide formation routes to ketene, acetaldehyde, ethanol, and vinyl alcohol (CH$_2$CHOH) along the H$_2$O formation sequence on grain surfaces. In this work, the non-energetic formation scheme is extended with laboratory measurements focusing on the energetic counterpart, induced by cosmic rays penetrating the H$_2$O-rich ice mantle. The focus here is on the H$^+$ radiolysis of interstellar C$_2$H$_2$:H$_2$O ice analogs at 17 K. Ultra-high vacuum experiments were performed to investigate the 200 keV H$^+$ radiolysis chemistry of predeposited C$_2$H$_2$:H$_2$O ices, both as mixed and layered geometries. Fourier-transform infrared spectroscopy was used to monitor in situ newly formed species as a function of the accumulated energy dose (or H$^+$ fluence). The infrared (IR) spectral assignments are further confirmed in isotope labeling experiments using H$_2$$^{18}$O. The energetic processing of C$_2$H$_2$:H$_2$O ice not only results in the formation of (semi-) saturated hydrocarbons (C$_2$H$_4$ and C$_2$H$_6$) and polyynes as well as cumulenes (C$_4$H$_2$ and C$_4$H$_4$), but it also efficiently forms O-bearing COMs, including vinyl alcohol, ketene, acetaldehyde, and ethanol, for which the reaction cross-section and product composition are derived. A clear composition transition of the product, from H-poor to H-rich species, is observed as a function of the accumulated energy dose.

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K. Chuang, G. Fedoseev, C. Scirè, et. al.
Tue, 20 Apr 2021
29/72

Comments: 14 pages, 7 figures, 2 tables

Phase Diagram for the Methane-Ethane System and its Implications for Titan's Lakes [EPA]

http://arxiv.org/abs/2103.15978


On Titan, methane (CH4) and ethane (C2H6) are the dominant species found in the lakes and seas. In this study, we have combined laboratory work and modeling to refine the methane-ethane binary phase diagram at low temperatures and probe how the molecules interact at these conditions. We used visual inspection for the liquidus and Raman spectroscopy for the solidus. Through these methods we determined a eutectic point of 71.15$\pm$0.5 K at a composition of 0.644$\pm$0.018 methane – 0.356$\pm$0.018 ethane mole fraction from the liquidus data. Using the solidus data, we found a eutectic isotherm temperature of 72.2 K with a standard deviation of 0.4 K. In addition to mapping the binary system, we looked at the solid-solid transitions of pure ethane and found that, when cooling, the transition of solid I-III occurred at 89.45$\pm$0.2 K. The warming sequence showed transitions of solid III-II occurring at 89.85$\pm$0.2 K and solid II-I at 89.65$\pm$0.2 K. Ideal predictions were compared to molecular dynamics simulations to reveal that the methane-ethane system behaves almost ideally, and the largest deviations occur as the mixing ratio approaches the eutectic composition.

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A. Engle, J. Hanley, S. Dustrud, et. al.
Wed, 31 Mar 2021
9/62

Comments: Accepted to The Planetary Science Journal: 2021-03-16

Toward a global model of the interactions in low-lying states of methyl cyanide: rotational and rovibrational spectroscopy of the $v_4 = 1$ state and tentative interstellar detection of the $v_4 = v_8 = 1$ state in Sgr B2(N) [GA]

http://arxiv.org/abs/2103.07389


New and existing rotational spectra of methyl cyanide were analyzed to extend the global model of low-lying vibrational states and their interactions to $v_4=1$ at 920 cm$^{-1}$. The rotational spectra cover large portions of the 36$-$1439 GHz region and reach quantum numbers $J$ and $K$ of 79 and 16, respectively. Information on the $K$ level structure of CH$_3$CN is obtained from IR spectra. A spectrum of $2\nu_8$ around 717 cm$^{-1}$, analyzed in our previous study, covered also the $\nu_4$ band. The assignments in this band cover 880$-$952 cm$^{-1}$, attaining quantum numbers $J$ and $K$ of 61 and 13, respectively.
The most important interaction of $v_4=1$ appears to be with $v_8=3$, $\Delta K=0$, $\Delta l=+3$, a previously characterized anharmonic resonance. We report new analyses of interactions with $\Delta K=-2$ and $\Delta l=+1$, with $\Delta K=-4$ and $\Delta l=-1$, and with $\Delta K=-6$ and $\Delta l=-3$; these four types of interactions connect all $l$ substates of $v_8=3$ in energy to $v_4=1$. A known $\Delta K=-2$, $\Delta l=+1$ interaction with $v_7=1$ was also analyzed, and investigations of the $\Delta K=+1$, $\Delta l=-2$ and $\Delta K=+3$, $\Delta l=0$ resonances with $v_8=2$ were improved, as were interactions between successive states with $v_8\le 3$, mainly through new $v_8\le 2$ rotational data.
A preliminary single state analysis of the $v_4=v_8=1$ state was carried out based on rotational transition frequencies and on $\nu_4+\nu_8-\nu_8$ hot band data. A considerable fraction of the $K$ levels was reproduced within uncertainties in its entirety or in part, despite obvious widespread perturbations in $v_4=v_8=1$.
We detect rotational transitions of methyl cyanide from within all vibrational states up to $v_4=1$ and $v_4=v_8=1$ tentatively toward the hot molecular core of Sagittarius B2(N) employing the Atacama Large Millimeter Array.

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H. Müller, A. Belloche, F. Lewen, et. al.
Mon, 15 Mar 21
13/36

Comments: 30 pages, J. Mol. Spectrosc., accepted

Photodissociation of aliphatic PAH derivatives under relevant astrophysical conditions [GA]

http://arxiv.org/abs/2103.03890


The interaction of polycyclic aromatic hydrocarbons (PAHs) with vacuum ultraviolet (VUV) photons triggers the emission of the well-known aromatic infrared bands but other mechanisms such as fragmentation can be involved in this interaction. Fragmentation leads to selection effects favoring specific sizes and structures. We investigate the impact of aliphatic bonds on the VUV photo-stability of PAH cations under conditions applicable for photodissociation regions (PDRs). Cations of pyrene (C16H10) and coronene (C24H12) derivatives containing aliphatic bonds (methyl or ethyl sidegroups, superhydrogenation) are submitted to VUV (10.5 eV) photons over long timescales (~1000 s) in the cryogenic PIRENEA setup. The fragmentation cascades are analyzed with a simple kinetics model; fragmentation pathways, rates and branching ratios are derived. Aliphatic PAH derivatives are found to have a higher fragmentation rate and carbon loss compared to regular PAHs. The fragmentation of PAHs with alkylated sidegroups forms species with peripheral pentagonal cycles, which can be more stable than the bare PAH cations. This stability is quantified and the most stable species, for which there is an effective competition of fragmentation with isomerization and radiative cooling, are identified. This work supports a scenario in which the evaporation of nanograins with mixed aliphatic and aromatic composition followed by VUV photoprocessing results in both the production of the carriers of the 3.4um AIB by methyl sidegroups and in an abundant source of small hydrocarbons at the border of PDRs. An additional side effect is the efficient formation of stable PAHs containing some peripheral pentagonal rings. Our experiments also support the role of isomerization processes in PAH photofragmentation, including the H-migration process, which could lead to an additional contribution to the 3.4um AIB.

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A. Marciniak, C. Joblin, G. Mulas, et. al.
Tue, 9 Mar 21
4/68

Comments: subbitted for publication on Astronomy and Astrophysics

ExoMol line lists — XLI. High-temperature molecular line lists for the alkali metal hydroxides KOH and NaOH [EPA]

http://arxiv.org/abs/2103.01601


Potassium hydroxide (KOH) and sodium hydroxide (NaOH) are expected to occur in the atmospheres of hot rocky super-Earth exoplanets but a lack of spectroscopic data is hampering their potential detection. Using robust first-principles methodologies, comprehensive molecular line lists for KOH and NaOH that are applicable for temperatures up to $T=3500$ K are presented. The KOH OYT4 line list covers the 0-6000 cm$^{-1}$ (wavelengths $\lambda > 1.67$ $\mu$m) range and comprises 38 billion transitions between 7.3 million energy levels with rotational excitation up to $J=255$. The NaOH OYT5 line list covers the 0 – 9000 cm$^{-1}$ (wavelengths $\lambda > 1.11$ $\mu$m) range and contains almost 50 billion lines involving 7.9 million molecular states with rotational excitation up to $J=206$. The OYT4 and OYT5 line lists are available from the ExoMol database at www.exomol.com and should greatly aid the study of hot rocky exoplanets.

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A. Owens, J. Tennyson and S. Yurchenko
Wed, 3 Mar 21
49/82

Comments: N/A

Near-resonant effects in the quantum dynamics of the H+H$_2^+$ $\rightarrow$ H$_2$+ H$^+$ charge transfer reaction and isotopic variants [CL]

http://arxiv.org/abs/2102.10930


The non-adiabatic quantum dynamics of the H+H$_2^+$ $\rightarrow$ H$_2$+ H$^+$ charge transfer reactions, and some isotopic variants, is studied with an accurate wave packet method. A recently developed $3\times$3 diabatic potential model is used, which is based on very accurate {\it ab initio} calculations and includes the long-range interactions for ground and excited states. It is found that for initial H$_2^+$(v=0), the quasi-degenerate H$_2$(v’=4) non-reactive charge transfer product is enhanced, producing an increase of the reaction probability and cross section. It becomes the dominant channel from collision energies above 0.2 eV, producing a ratio, between v’=4 and the rest of v’s, that increases up to 1 eV. H+H$_2^+$ $\rightarrow$ H$_2^+$+ H exchange reaction channel is nearly negligible, while the reactive and non-reactive charge transfer reaction channels are of the same order, except that corresponding to H$_2$(v’=4), and the two charge transfer processes compete below 0.2 eV. This enhancement is expected to play an important vibrational and isotopic effect that need to be evaluated. For the three proton case, the problem of the permutation symmetry is discussed when using reactant Jacobi coordinates.

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C. Sanz-Sanz, A. Aguado and O. Roncero
Tue, 23 Feb 21
43/79

Comments: 13 pages, 7 figures, Accepted for publication in J. Chem. Phys. (2021)

Meteoritic Proteins with Glycine, Iron and Lithium [CL]

http://arxiv.org/abs/2102.10700


We report that polymer amide [1] with a protein backbone of mainly glycine units and iron is present in the CV3 meteorites Acfer 086, Allende and KABA. The evidence for this is from particles of these meteorites after Folch extraction being analyzed by MALDI mass spectrometry and from the 3D physical structures that form in the various Folch solvent phases. The two physical forms we observe are branching rods and entrapping spheres on the 100micron scale. Two potential molecular structures of polymer amide are presented in this report. One we term hemolithin of mass 2320Da, contains glycine, hydroxy-glycine, Fe, O and Li. The other, we term hemoglycin of mass 1494Da is of glycine, hydroxy-glycine, Fe and O. Hemoglycin is connected covalently in triplets by silicon to form a triskelion. Analysis of the complete spectrum of isotopes associated with each molecular fragment shows very high 2H enhancement above terrestrial averaging 25,700 parts per thousand (sigma = 3,500, n=15), confirming extra-terrestrial origin and hence the existence of these molecules within the asteroid parent body of the CV3 meteorite class. The hemoglycin triskelia join via silicon bonds into an extended lattice, as seen in mass spectrometry of lattice fragments at m/z 4641 and above [2]. The identification of hemolithin and hemoglycin required careful methodology at room temperature with the minimum of steps up to mass spectrometry analysis ensuring that only the laser step fragmented the molecules. The 3D structures were imaged through permanently closed Folch extraction V-vials at a magnification of 10.

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M. McGeoch, S. Dikler and J. McGeoch
Tue, 23 Feb 21
69/79

Comments: arXiv admin note: substantial text overlap with arXiv:2002.11688

An improved rovibrational linelist of formaldehyde, \spec{h212c16o} [SSA]

http://arxiv.org/abs/2102.07423


Published high-resolution rotation-vibration transitions of \spec{h212c16o}, the principal isotopologue of methanal, are analyzed using the MARVEL (Measured Active Rotation-Vibration Energy Levels) procedure. The literature results are augmented by new, high-accuracy measurements of pure rotational transitions within the ground, $\nu_3$, $\nu_4$, and $\nu_6$ vibrational states. Of the \nbNonRedTr\ non-redundant transitions processed, which come from \nbSr\ sources including the present work, \nbValTr\ could be validated, providing \nbEl\ empirical energy levels of \spec{h212c16o}\ with statistically well-defined uncertainties. All the empirical rotational-vibrational energy levels determined are used to improve the accuracy of ExoMol’s AYTY line list for hot formaldehyde. The complete list of collated experimental transitions, the empirical energy levels determined, as well as the extended and improved line list are provided as Supplementary Material.

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A. Al-Derzi, J. Tennyson, S. Yurchenko, et. al.
Tue, 16 Feb 21
43/63

Comments: Accepted for publication on the HITRAN special issue of J. Quant. Spectrosc. Radiat. Transf. (2021)

Modeling Anharmonic Infrared Spectra of Thermally Excited Pyrene(C$_{16}$H$_{10}$): the combined view of DFT AnharmonicCaOs and approximate DFT molecular dynamics [GA]

http://arxiv.org/abs/2102.06582


Aromatic Infrared Bands (AIBs) are a set of bright and ubiquitous emission bands, observed in regions illuminated by stellar ultraviolet photons, from our galaxy all the way out to cosmological distances. The forthcoming James Webb Space Telescope will unveil unprecedented spatial and spectral details in the AIB spectrum; significant advancement is thus necessary now to model the infrared emission of polycyclic aromatic hydrocarbons, their presumed carriers, with enough detail to exploit the information content of the AIBs. This requires including anharmonicity in such models, and to do so systematically for all species included, requiring a difficult compromise between accuracy and efficiency. We propose a new recipe using minimal assumptions on the general behaviour of band positions and widths with temperature, which can be defined by a small number of empirical parameters. We explore here the performances of a full quantum method, AnharmoniCaOs, relying on an ab initio potential, and Molecular Dynamics simulations using a Density Functional based Tight Binding potential to determine these parameters for the case of pyrene, for which high temperature gas-phase data are available. The first one is very accurate and detailed, but it becomes computationally very expensive for increasing T; the second trades some accuracy for speed, making it suitable to provide approximate, general trends at high temperatures. We propose to use, for each species and band, the best available empirical parameters for a fast, yet sufficiently accurate spectral model of PAH emission properly including anharmonicity. Modelling accuracy will depend critically on these empirical parameters, allowing for an incremental improvement in model results, as better estimates become gradually available.

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S. Chakraborty, G. Mulas, M. Rapacioli, et. al.
Mon, 15 Feb 21
28/53

Comments: submitted to the Journal of Molecular Spectroscopy

IR photofragmentation of the Phenyl Cation: Spectroscopy and Fragmentation Pathways [CL]

http://arxiv.org/abs/2102.06420


We present the gas-phase infrared spectra of the phenyl cation, phenylium, in its perprotio C$_6$H$_5^+$ and perdeutero C$_6$D$_5^+$ forms, in the 260-1925 cm$^{-1}$ (5.2-38 $\mu$m) spectral range, and investigate the observed photofragmentation. The spectral and fragmentation data were obtained using Infrared Multiple Photon Dissociation (IRMPD) spectroscopy within a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer (FTICR MS) located inside the cavity of the free electron laser FELICE (Free Electron Laser for Intra-Cavity Experiments). The $^1$A$_1$ singlet nature of the phenylium ion is ascertained by comparison of the observed IR spectrum with DFT calculations, using both harmonic and anharmonic frequency calculations. To investigate the observed loss of predominantly [2C,nH] (n=2-4) fragments, we explored the potential energy surface (PES) to unravel possible isomerization and fragmentation reaction pathways. The lowest energy pathways toward fragmentation include direct H elimination, and a combination of facile ring-opening mechanisms ($\leq2.4$ eV), followed by elimination of H or CCH$_2$. Energetically, all H-loss channels found are more easily accessible than CCH$_2$-loss. Calculations of the vibrational density of states for the various intermediates show that at high internal energies, ring opening is the thermodynamically the most advantageous, eliminating direct H-loss as a competing process. The observed loss of primarily [2C,2H] can be explained through entropy calculations that show favored loss of [2C,2H] at higher internal energies.

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S. Wiersma, A. Candian, J. Bakker, et. al.
Mon, 15 Feb 21
34/53

Comments: 10 pages, 6 figures and 1 table. Accepted for publication on PCCP on 04 Feb 2021; supplementary Material available on PCCP website

Rotational spectroscopy of isotopic cyclopropenone, $c$-H$_2$C$_3$O, and determination of its equilibrium structure [IMA]

http://arxiv.org/abs/2102.03570


Cyclopropenone was first detected in the cold and less dense envelope of Sagittarius B2(N). It was found later in several cold dark clouds and it may be possible to detect its minor isotopic species in these environments. In addition, the main species may well be identified in warmer environments. We aim to extend existing line lists of isotopologs of c-H2C3O from the microwave to the millimeter region and create one for the singly deuterated isotopolog to facilitate their detections in space. Furthermore, we aim to extend the line list of the main isotopic species to the submillimeter region and to evaluate an equilibrium structure of the molecule. We employed a cyclopropenone sample in natural isotopic composition to investigate the rotational spectra of the main and 18O-containing isotopologs as well as the two isotopomers containing one 13C atom. Spectral recordings of the singly and doubly deuterated isotopic species were obtained using a cyclopropenone sample highly enriched in deuterium. We recorded rotational transitions in the 70-126 GHz and 160-245 GHz regions for all isotopologs and also in the 342-505 GHz range for the main species. Quantum-chemical calculations were carried out to evaluate initial spectroscopic parameters and the differences between ground-state and equilibrium rotational parameters in order to derive semi-empirical equilibrium structural parameters. We determined new or improved spectroscopic parameters for six isotopologs and structural parameters according to different structure models. The spectroscopic parameters are accurate enough to identify minor isotopic species at centimeter and millimeter wavelengths while those of the main species are deemed to be reliable up to 1 THz. Our structural parameters differ from earlier ones. The deviations are attributed to misassignments in the earlier spectrum of one isotopic species.

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H. Müller, A. M., J. Guillemin, et. al.
Tue, 9 Feb 21
11/87

Comments: 11 pages; abstract slightly abbreviated; Astron. Astrophys., in press

A rotational and vibrational investigation of phenylpropiolonitrile (C$_6$H$_5$C$_3$N) [GA]

http://arxiv.org/abs/2101.11534


The evidence for benzonitrile (C$_6$H$_5$CN}) in the starless cloud core TMC-1 makes high-resolution studies of other aromatic nitriles and their ring-chain derivatives especially timely. One such species is phenylpropiolonitrile (3-phenyl-2-propynenitrile, C$_6$H$_5$C$_3$N), whose spectroscopic characterization is reported here for the first time. The low resolution (0.5 cm$^{-1}$) vibrational spectrum of C$_6$H$_5$C$_3$N} has been recorded at far- and mid-infrared wavelengths (50 – 3500 cm$^{-1}$) using a Fourier Transform interferometer, allowing for the assignment of band centers of 14 fundamental vibrational bands. The pure rotational spectrum of the species has been investigated using a chirped-pulse Fourier transform microwave (FTMW) spectrometer (6 – 18 GHz), a cavity enhanced FTMW instrument (6 – 20 GHz), and a millimeter-wave one (75 – 100 GHz, 140 – 214 GHz). Through the assignment of more than 6200 lines, accurate ground state spectroscopic constants (rotational, centrifugal distortion up to octics, and nuclear quadrupole hyperfine constants) have been derived from our measurements, with a plausible prediction of the weaker bands through calculations. Interstellar searches for this highly polar species can now be undertaken with confidence since the astronomically most interesting radio lines have either been measured or can be calculated to very high accuracy below 300 GHz.

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Z. Buchanan, K. Lee, O. Chitarra, et. al.
Thu, 28 Jan 21
56/64

Comments: 7 figures, 4 tables. Accepted for publication in J. Mol. Spec

Sulfur Chemistry in the Atmospheres of Warm and Hot Jupiters [EPA]

http://arxiv.org/abs/2101.08327


We present and validate a new network of atmospheric thermo-chemical and photo-chemical sulfur reactions. We use a 1-D chemical kinetics model to investigate these reactions as part of a broader HCNO chemical network in a series of hot and warm Jupiters. We find that temperatures approaching $1400\,\mathrm{K}$ are favourable for the production of H2S and HS around $\mathrm{10^{-3}\,bar}$, the atmospheric level where detection by transit spectroscopy may be possible, leading to mixing ratios of around $10^{-6}$. At lower temperatures, down to $1000\,\mathrm{K}$, the abundance of S2 can be up to a mixing ratio of $10^{-5}$ at the same pressure, at the expense of H2S and HS, which are depleted down to a mixing ratio of $10^{-6}$. We also investigate how the inclusion of sulfur can manifest in an atmosphere indirectly, by its effect on the abundance of non-sulfur-bearing species. We find that in a model of the atmosphere of HD 209458 b, the inclusion of sulfur can lower the abundance of NH3, CH4 and HCN by up to two orders of magnitude around $\mathrm{10^{-3}\,bar}$. In the atmosphere of the warm Jupiter 51 Eri b, we additionally find the inclusion of sulphur depletes the peak abundance of CO2 by a factor of five, qualitatively consistent with prior models. We note that many of the reactions used in the network have poorly determined rates, especially at higher temperatures. To obtain a truly accurate idea of the impact of sulfur chemistry in hot and warm Jupiter atmospheres, new measurements of these reaction rates must take place.

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R. Hobbs, P. Rimmer, O. Shorttle, et. al.
Fri, 22 Jan 21
29/69

Comments: 17 pages, 9 Figures

Metallization of Shock-Compressed Liquid Ammonia [EPA]

http://arxiv.org/abs/2101.06692


Ammonia is predicted to be one of the major components in the depths of the ice giant planets Uranus and Neptune. Their dynamics, evolution, and interior structure are insufficiently understood and models rely imperatively on data for equation of state and transport properties. Despite its great significance, the experimentally accessed region of the ammonia phase diagram today is still very limited in pressure and temperature. Here we push the probed regime to unprecedented conditions, up to $\sim$350 GPa and $\sim$40000 K. Along the Hugoniot, the temperature measured as a function of pressure shows a subtle change in slope at $\sim$7000 K and $\sim$90 GPa, in agreement with ab initio simulations we have performed. This feature coincides with the gradual transition from a molecular liquid to a plasma state. Additionally, we performed reflectivity measurements, providing the first experimental evidence of electronic conduction in high-pressure ammonia. Shock reflectance continuously rises with pressure above 50 GPa and reaches saturation values above 120 GPa. Corresponding electrical conductivity values are up to 1 order of magnitude higher than in water in the 100 GPa regime, with possible significant contributions of the predicted ammonia-rich layers to the generation of magnetic dynamos in ice giant interiors.

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A. Ravasio, M. Bethkenhagen, J. Hernandez, et. al.
Tue, 19 Jan 21
32/92

Comments: Please visit publisher’s website for supplementary information

2-aminooxazole in astrophysical environments: IR spectra and destruction cross sections for energetic processing [IMA]

http://arxiv.org/abs/2101.06164


2-aminooxazole (2AO), a N-heterocyclic molecule, has been proposed as an intermediate in prebiotic syntheses. It has been demonstrated that it can be synthesized from small molecules such as cyanamide and glycoaldehyde, which are present in interstellar space. The aim of this work is to provide infrared spectra, in the solid phase for conditions typical of astrophysical environments and to estimate its stability toward UV photons and cosmic rays. Infrared (4000-600 cm$^{-1}$) absorption spectra at 20 K, 180 K, and 300 K, IR band strengths, and room temperature UV (120-250 nm) absorption spectra are given for the first time for this species. Destruction cross-sections of 9.5 10$^{-18}$ cm$^2$ and 2 10$^{-16}$ cm$^2$ were found in the irradiation at 20 K of pure 2AO and 2AO:H$_2$O ices with UV (6.3-10.9 eV) photons or 5 keV electrons, respectively. These data were used for the estimate of half-life times for the molecule in different environments. It is estimated that 2AO could survive UV radiation and cosmic rays in the ice mantles of dense clouds beyond cloud collapse. In contrast, it would be very unstable at the surface of cold Solar System bodies like Kuiper belt objects, but the molecule could still survive within dust grain agglomerates or cometesimals.

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B. Maté, R. Carrasco-Herrera, V. Timón, et. al.
Mon, 18 Jan 21
9/41

Comments: 31 pages, 9 figures. Accepted to be published in The Astrophysical Journal

A New Method for Simulating Photoprocesses in Astrochemical Models [GA]

http://arxiv.org/abs/2101.01209


We propose a new model for treating solid-phase photoprocesses in interstellar ice analogues. In this approach, photoionization and photoexcitation are included in more detail, and the production of electronically-excited (suprathermal) species is explicitly considered. In addition, we have included non-thermal, non-diffusive chemistry to account for the low-temperature characteristic of cold cores. As an initial test of our method, we have simulated two previous experimental studies involving the UV irradiation of pure solid O$_2$. In contrast to previous solid-state astrochemical model calculations which have used gas-phase photoabsorption cross-sections, we have employed solid-state cross-sections in our calculations. This method allows the model to be tested using well-constrained experiments rather than poorly constrained gas-phase abundances in ISM regions. Our results indicate that inclusion of non-thermal reactions and suprathermal species allows for reproduction of low-temperature solid-phase photoprocessing that simulate interstellar ices within cold ($\sim$ 10 K) dense cores such as TMC-1.

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E. Mullikin, H. Anderson, N. O’Hern, et. al.
Wed, 6 Jan 21
35/82

Comments: ApJ, accepted: 15 pages, 3 figures

Cosmology, astrobiology, and the RNA world. Just add quintessential water [CL]

http://arxiv.org/abs/2012.12079


Water nanoclusters ejected into interstellar space from abundant amorphous ice-coated cosmic dust offer a hypothetical scenario connecting major mysteries of our universe: dark matter, dark energy, cosmology, astrobiology, and the RNA world.

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K. Johnson
Wed, 23 Dec 20
6/72

Comments: 25 pages; 10 figures

MOVES IV. Modelling the influence of stellar XUV-flux, cosmic rays, and stellar energetic particles on the atmospheric composition of the hot Jupiter HD 189733b [EPA]

http://arxiv.org/abs/2012.12132


Hot Jupiters provide valuable natural laboratories for studying potential contributions of high-energy radiation to prebiotic synthesis in the atmospheres of exoplanets. In this fourth paper of the MOVES (Multiwavelength Observations of an eVaporating Exoplanet and its Star) programme, we study the effect of different types of high-energy radiation on the production of organic and prebiotic molecules in the atmosphere of the hot Jupiter HD 189733b. Our model combines X-ray and UV observations from the MOVES programme and 3D climate simulations from the 3D Met Office Unified Model to simulate the atmospheric composition and kinetic chemistry with the STAND2019 network. Also, the effects of galactic cosmic rays and stellar energetic particles are included. We find that the differences in the radiation field between the irradiated dayside and the shadowed nightside lead to stronger changes in the chemical abundances than the variability of the host star’s XUV emission. We identify ammonium (NH4+) and oxonium (H3O+) as fingerprint ions for the ionization of the atmosphere by both galactic cosmic rays and stellar particles. All considered types of high-energy radiation have an enhancing effect on the abundance of key organic molecules such as hydrogen cyanide (HCN), formaldehyde (CH2O), and ethylene (C2H4). The latter two are intermediates in the production pathway of the amino acid glycine (C2H5NO2) and abundant enough to be potentially detectable by JWST.

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P. Barth, C. Helling, E. Stüeken, et. al.
Wed, 23 Dec 20
13/72

Comments: Accepted by MNRAS, 15 pages, 11 figures, 4 tables

Detectability of biosignatures on LHS 1140 b [EPA]

http://arxiv.org/abs/2012.11426


Terrestrial extrasolar planets around low-mass stars are prime targets when searching for atmospheric biosignatures with current and near-future telescopes. The habitable-zone Super-Earth LHS 1140 b could hold a hydrogen-dominated atmosphere and is an excellent candidate for detecting atmospheric features. In this study, we investigate how the instellation and planetary parameters influence the atmospheric climate, chemistry, and spectral appearance of LHS 1140 b. We study the detectability of selected molecules, in particular potential biosignatures, with the upcoming James Webb Space Telescope (JWST) and Extremely Large Telescope (ELT). In a first step we use the coupled climate-chemistry model, 1D-TERRA, to simulate a range of assumed atmospheric chemical compositions dominated by H$_2$ and CO$_2$. Further, we vary the concentrations of CH$_4$ by several orders of magnitude. In a second step we calculate transmission spectra of the simulated atmospheres and compare them to recent transit observations. Finally, we determine the observation time required to detect spectral bands with low resolution spectroscopy using JWST and the cross-correlation technique using ELT. In H$_2$-dominated and CH$_4$-rich atmospheres O$_2$ has strong chemical sinks, leading to low concentrations of O$_2$ and O$_3$. The potential biosignatures NH$_3$, PH$_3$, CH$_3$Cl and N$_2$O are less sensitive to the concentration of H$_2$, CO$_2$ and CH$_4$ in the atmosphere. In the simulated H$_2$-dominated atmosphere the detection of these gases might be feasible within 20 to 100 observation hours with ELT or JWST, when assuming weak extinction by hazes. If further observations of LHS 1140 b suggest a thin, clear, hydrogen-dominated atmosphere, the planet would be one of the best known targets to detect biosignature gases in the atmosphere of a habitable-zone rocky exoplanet with upcoming telescopes.

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F. Wunderlich, M. Scheucher, J. Grenfell, et. al.
Tue, 22 Dec 20
71/89

Comments: 18 pages, 11 figures

Electric-quadrupole and magnetic-dipole contributions to the n2+n3 band of carbon dioxide near 3.3 micron [CL]

http://arxiv.org/abs/2012.07518


The recent detections of electric-quadrupole (E2) transitions in water vapor and magnetic-dipole (M1) transitions in carbon dioxide have opened a new field in molecular spectroscopy. While in their present status, the spectroscopic databases provide only electric-dipole (E1) transitions for polyatomic molecules (H2O, CO2, N2O, CH4, O3), the possible impact of weak E2 and M1 bands to the modeling of the Earth and planetary atmospheres has to be addressed. This is especially important in the case of carbon dioxide for which E2 and M1 bands may be located in spectral windows of weak E1 absorption. In the present work, a high sensitivity absorption spectrum of CO2 was recorded by optical feedback cavity enhanced absorption Spectroscopy (OFCEAS) in the 3.3 micron transparency window of carbon dioxide. The studied spectral interval corresponds to the region where M1 transitions of the n2+n3 band of carbon dioxide were recently identified in the spectrum of the Martian atmosphere. Here, both M1 and E2 transitions of the n2+n3 band were detected by OFCEAS. Using recent ab initio calculations of the E2 spectrum of 12C16O2, intensity measurements of five M1 lines and three E2 lines allow us to disentangle the M1 and E2 contributions. Indeed, E2 intensity values (on the order of a few 10-29 cm per molecule) are found in reasonable agreement with ab initio calculations while the intensity of the M1 lines (including an E2 contribution) agree very well with recent very long path measurements by Fourier Transform spectroscopy. We thus conclude that both E2 and M1 transitions should be systematically incorporated in the CO2 line list provided by spectroscopic databases.

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H. Fleurbaey, R. Grilli, D. Mondelain, et. al.
Tue, 15 Dec 20
49/136

Comments: N/A

Theoretical kinetic studies of Venus chemistry. Formation and destruction of SCl, SCl2, and HSCl [CL]

http://arxiv.org/abs/2012.02054


Accurate and thorough characterization of the chemistry of compounds containing the third-row elements sulfur and chlorine is critical for modeling the composition of the atmosphere of Venus. We have used a combination of ab initio quantum chemistry and kinetic theory to characterize a group of nine exothermic reactions that involve the exotic sulfur-chlorine species SCl, SCl2, and HSCl, which are thought to be present in trace quantities in the atmosphere of Venus and are included to various degrees in the published atmospheric models. Reaction pathways were characterized with coupled cluster theory at the RCCSD(T) level with triple zeta quality correlation consistent basis sets. For reactions with barriers that lie above the reactant asymptote, the barrier height was extrapolated to the RCCSD(T) complete basis set level via single-point calculations with quadruple and quintuple zeta quality sets. Rate coefficients were predicted with capture theory and transition state theory as appropriate. We have found that in some cases addition-elimination reactions can compete with abstraction reactions due to the tendency of sulfur to form hypervalent compounds and intermediates via recoupled pair bonding.

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D. Woon, D. Maffucci and E. Herbst
Fri, 4 Dec 20
23/77

Comments: Includes 3 tables and 5 figures, plus Supplemental Information (cartesian structures, energies, and ZPE corrections)

Tunneling Enhancement of the Gas-Phase CH + CO2 Reaction at Low Temperature [GA]

http://arxiv.org/abs/2012.01234


The rates of numerous activated reactions between neutral species increase at low temperatures through quantum mechanical tunneling of light hydrogen atoms. Although tunneling processes involving molecules or heavy atoms are well known in the condensed phase, analogous gas-phase processes have never been demonstrated experimentally. Here, we studied the activated CH + CO2 -> HCO + CO reaction in a supersonic flow reactor, measuring rate constants that increase rapidly below 100 K. Mechanistically, tunneling is shown to occur by CH insertion into the C-O bond, with rate calculations accurately reproducing the experimental values. To exclude the possibility of H-atom tunneling, CD was used in additional experiments and calculations. Surprisingly, the equivalent CD + CO2 reaction accelerates at low temperature as zero point energy effects remove the barrier to product formation. In conclusion, heavy-particle tunneling effects might be responsible for the observed reactivity increase at lower temperatures for the CH + CO2 reaction, while the equivalent effect for the CD + CO2 reaction results instead from a submerged barrier with respect to reactants.

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D. Nunez-Reyes, K. Hickson, J. Loison, et. al.
Thu, 3 Dec 20
55/81

Comments: Accepted for publication in the Journal of Physical Chemistry A. 30 pages including supplementary materials

Evolution and Mass Loss of Cool Ageing Stars: a Daedalean Story [SSA]

http://arxiv.org/abs/2011.13472


The chemical enrichment of the Universe; the mass spectrum of planetary nebulae, white dwarfs and gravitational wave progenitors; the frequency distribution of Type I and II supernovae; the fate of exoplanets … a multitude of phenomena which is highly regulated by the amounts of mass that stars expel through a powerful wind. For more than half a century, these winds of cool ageing stars have been interpreted within the common interpretive framework of 1-dimensional (1D) models. I here discuss how that framework now appears to be highly problematic.
* Current 1D mass-loss rate formulae differ by orders of magnitude, rendering contemporary stellar evolution predictions highly uncertain.
These stellar winds harbour 3D complexities which bridge 23 orders of magnitude in scale, ranging from the nanometer up to thousands of astronomical units. We need to embrace and understand these 3D spatial realities if we aim to quantify mass loss and assess its effect on stellar evolution. We therefore need to gauge
* the 3D life of molecules and solid-state aggregates: the gas-phase clusters that form the first dust seeds are not yet identified. This limits our ability to predict mass-loss rates using a self-consistent approach.
* the emergence of 3D clumps: they contribute in a non-negligible way to the mass loss, although they seem of limited importance for the wind-driving mechanism.
* the 3D lasting impact of a (hidden) companion: unrecognised binary interaction has biased previous mass-loss rate estimates towards values that are too large.
Only then will it be possible to drastically improve our predictive power of the evolutionary path in 4D (classical) spacetime of any star.

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L. Decin
Mon, 30 Nov 20
85/117

Comments: preprint of invited review article to be published in the Annual Review of Astronomy and Astrophysics (2021) – 71 pages, Main Paper 58 pages, Supplemental Material 13 pages, 10 figures of which Figure 8 is also a movie. Movie does not display properly in all pdf file readers; therefore the movie has been uploaded separately or can be obtained via request to the author

A Kinetic Study of the N(2D) + C2H4 Reaction at Low Temperature [CL]

http://arxiv.org/abs/2012.00655


Electronically excited nitrogen atoms N(2D) are important species in the photochemistry of N2 based planetary atmospheres such as Titan. Despite this, few N(2D) reactions have been studied over the appropriate low temperature range. During the present work, rate constants were measured for the N(2D) + ethene (C2H4) reaction using a supersonic flow reactor at temperatures between 50 K and 296 K. Here, a chemical reaction was used to generate N(2D) atoms, which were detected directly by laser induced fluorescence in the vacuum ultraviolet wavelength region. The measured rate constants displayed very little variation as a function of temperature, with substantially larger values than those obtained in previous work. Indeed, considering an average temperature of 170 K for the atmosphere of Titan leads to a rate constant that is almost seven times larger than the currently recommended value. In parallel, electronic structure calculations were performed to provide insight into the reactive process. While earlier theoretical work at a lower level predicted the presence of a barrier for the N(2D) + C2H4 reaction, the present calculations demonstrate that two of the five doublet potential energy surfaces correlating with reagents are likely to be attractive, presenting no barriers for the perpendicular approach of the N atom to the carbon double bond of ethene. The measured rate constants and new product channels taken from recent dynamical investigations of this process are included in a 1D coupled ion-neutral model of Titans atmosphere. These simulations indicate that the modeled abundances of numerous nitrogen bearing compounds are noticeably affected by these changes.

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K. Hickson, C. Bray, J. Loison, et. al.
Wed, 2 Dec 20
10/71

Comments: 21 pages, 5 figures, 2 tables

A new instrument for kinetics and branching ratio studies of gas phase collisional processes at very low temperatures [CL]

http://arxiv.org/abs/2012.00374


A new instrument dedicated to the kinetic study of low-temperature gas phase neutral-neutral reactions, including clustering processes, is presented. It combines a supersonic flow reactor with Vacuum Ultra-Violet (VUV) synchrotron photoionization time of flight mass spectrometry. A photoion-photoelectron coincidence detection scheme has been adopted to optimize the particle counting efficiency. The characteristics of the instrument are detailed along with its capabilities illustrated through a few results obtained at low temperatures (< 100 K) including a {photoionization spectrum} of n-butane, the detection of formic acid dimer formation as well as the observation of diacetylene molecules formed by the reaction between the C$_2$H radical and C$_2$H$_2$.

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O. Durif, M. Capron, J. Messinger, et. al.
Wed, 2 Dec 20
23/71

Comments: N/A

Natural radioactive environments as sources of local disequilibrium for the emergence of life [CL]

http://arxiv.org/abs/2011.14839


Certain subterranean environments of Earth have naturally accumulated long-lived radionuclides, such as 238U, 232Th and 40K, near the presence of liquid water. In these natural radioactive environments (NRE), water radiolysis can produce chemical species of biological importance, such as H2. Although the proposal of radioactive decay as an alternative source of energy for living systems has existed for more than thirty years, this hypothesis gained strength after the recent discovery of a peculiar ecosystem in a gold mine in South Africa, whose existence is dependent on chemical species produced by water radiolysis. In this work, we calculate the chemical disequilibrium generated locally by water radiolysis due gamma radiation and analyse the possible contribution of this disequilibrium for the emergence of life, considering conditions of early Earth and having as reference the alkaline hydrothermal vent (AHV) theory. Results from our kinetic model points out the similarities between the conditions caused by water radiolysis and those found on alkaline hydrothermal systems. Our model produces a steady increase of pH with time, which favours the precipitation of minerals with catalytic activity for protometabolism, as well as a natural electrochemical gradient in this aqueous environment. In conclusion, we described a possible free-energy conversion mechanism that could be a requisite for emergence of life in Hadean Earth.

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T. Altair, L. Sartori, F. Rodrigues, et. al.
Tue, 1 Dec 20
29/108

Comments: 51 pages, 9 figures, supplementary material included. Astrobiology

The Origin of Chiral Life [GA]

http://arxiv.org/abs/2011.12145


The phenomenon of life is discussed within a framework of its origin as defined by four hypotheses. The 1. hypothesis says: Life, as we know, is (H-C-N-O) based and relies on the number of bulk (Na-Mg-P-S-Cl-K-Ca) and trace elements (Cr-Mn-Fe-Co-Ni-Cu-Zn-Se-Mo-I-W, and possibly Li-B-F-Si-V-As). It originated when the element abundance curve of the living matter and of the Universe, coincided. The 2. hypothesis is: Life originated in an interstellar molecular cloud with the critical role of dust particles. The 3. hypothesis arises from the 1. and states: Because of the Universe ageing, life originated only once. The dust forming planetary system and stars already contained an excess of L-type amino acids and D-type sugars, therefore, the emerging life on any planet had to be chiral. Consequently, the 4. hypothesis has been formed: Chirality is a sine qua non-condition for the emergence of life. The arguments supporting these hypotheses are put forward based on numerous astrophysical observations and physics laws.

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V. Valkovic and J. Obhodas
Wed, 25 Nov 2020
9/65

Comments: 23 pages, 8 figures

The formation of glycolonitrile (HOCH$_2$CN) from reactions of C$^+$ with HCN and HNC on icy grain mantles [GA]

http://arxiv.org/abs/2011.12226


Quantum chemical cluster calculations show that reactions of C$^+$ with HCN or HNC embedded in the surface of an icy grain mantle can account for the formation of a recently detected molecule, glycolonitrile, which is considered to be an important precursor to ribonucleic compounds. Reactions of cations deposited on ice mantles with minimal kinetic energy have been found theoretically to result in previously unknown pathways to significant organic compounds in protostellar systems and the interstellar medium. In density functional theory cluster calculations involving up to 24H$_2$O, C$^+$ reacts consistently with HCN embedded in ice to yield the neutral HOCHNC radical with no barrier, along with H$_3$O+ as a byproduct. If HOCHNC then reacts with H, three species can be formed: HOCH$_2$CN (isocyanomethanol), HOCH$_2$CN (glycolonitrile), and HOCHNCH. For the C$^+$ + HNC reaction on ice, the HOCHCN and H$_2$OCCN radicals form as intermediates, the first of which is another direct precursor to glycolonitrile via H addition. In addition to characterizing reaction pathways, predictions are provided of the vibrational and electronic spectra of the HCN and HNC starting clusters and the HOCHNC ice-bound intermediate.

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D. Woon
Wed, 25 Nov 2020
49/65

Comments: Accepted for publication in ApJ. 5 figures. Includes supplemental information (cartesian coordinates, energies, ZPE)

Methanimine as a key precursor of imines in the interstellar medium: the case of propargylimine [GA]

http://arxiv.org/abs/2010.11651


A gas-phase formation route is proposed for the recently detected propargylimine molecule. In analogy to other imines, such as cyanomethanimine, the addition of a reactive radical (C$_2$H in the present case) to methanimine (CH$_2$NH}) leads to reaction channels open also in the harsh conditions of the interstellar medium. Three possible isomers can be formed in the C$H_2$NH + C$_2$H reaction: Z- and E-propargylimine (Z-,E-PGIM) as well as N-ethynyl-methanimine (N-EMIM). For both PGIM species, the computed global rate coefficient is nearly constant in the 20-300 K temperature range, and of the order of 2-3 $\times$ 10$^{-10}$ cm$^3$ molecule$^{-1}$ s$^{-1}$, while that for N-EMIM is about two orders of magnitude smaller. Assuming equal destruction rates for the two isomers, these results imply an abundance ratio for PGIM of [Z]/[E] $\sim$ 1.5, which is only slightly underestimated with respect to the observational datum.

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J. Lupi, C. Puzzarini and V. Barone
Fri, 23 Oct 20
63/67

Comments: 10 pages, 4 figures, 2 tables. Accepted in ApJL

CRAHCN-O: A Consistent Reduced Atmospheric Hybrid Chemical Network Oxygen Extension for Hydrogen Cyanide and Formaldehyde Chemistry in CO2-, N2-, H2O-, CH4-, and H2-Dominated Atmospheres [CL]

http://arxiv.org/abs/2009.12375


Hydrogen cyanide (HCN) and formaldehyde (H2CO) are key precursors to biomolecules such as nucleobases and amino acids in planetary atmospheres; However, many reactions which produce and destroy these species in atmospheres containing CO2 and H2O are still missing from the literature. We use a quantum chemistry approach to find these missing reactions and calculate their rate coefficients using canonical variational transition state theory and Rice-Ramsperger-Kassel-Marcus/master equation theory at the BHandHLYP/aug-cc-pVDZ level of theory. We calculate the rate coefficients for 126 total reactions, and validate our calculations by comparing with experimental data in the 39% of available cases. Our calculated rate coefficients are most frequently within an factor of 2 of experimental values, and generally always within an order of magnitude of these values. We discover 45 previously unknown reactions, and identify 6 from this list that are most likely to dominate H2CO and HCN production and destruction in planetary atmospheres. We highlight $^1$O + CH3 $\rightarrow$ H2CO + H as a new key source, and H2CO + $^1$O $\rightarrow$ HCO + OH as a new key sink, for H2CO in upper planetary atmospheres. In this effort, we develop an oxygen extension to our consistent reduced atmospheric hybrid chemical network (CRAHCN-O), building off our previously developed network for HCN production in N2-, CH4-, and H2-dominated atmospheres (CRAHCN). This extension can be used to simulate both HCN and H2CO production in atmospheres dominated by any of CO2, N2, H2O, CH4, and H2.

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B. Pearce, P. Ayers and R. Pudritz
Wed, 30 Sep 2020
18/86

Comments: Accepted for publication in J Phys Chem A, 21 pages, 4 tables, 35 supplementary pages

Atom-Tunneling in Chemistry [CL]

http://arxiv.org/abs/2009.04303


Quantum mechanical tunneling of atoms is increasingly found to play an important role in many chemical transformations. Experimentally, atom-tunneling can be indirectly detected by temperature-independent rate constants at low temperature or by enhanced kinetic isotope effects. On the contrary, using computational investigations the influence of tunneling on the reaction rates can directly be monitored. The tunnel effect, for example, changes reaction paths and branching ratios, enables chemical reactions in an astrochemical environment that would be impossible by thermal transition, and influences biochemical processes.

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J. Meisner and J. Kästner
Thu, 10 Sep 20
-1493/82

Comments: N/A

Computational insight into diatomic molecules as probes to measure the variation of the proton-to-electron mass ratio [CL]

http://arxiv.org/abs/2008.10799


Astrophysical molecular spectroscopy is an important means of searching for new physics through probing the variation of the proton-to-electron mass ratio, $\mu$. New molecular probes could provide tighter constraints on the variation of $\mu$ and better direction for theories of new physics. Here we summarise our previous paper \citep{19SyMoCu.CN} for astronomers, highlighting the importance of accurate estimates of peak molecular abundance and temperature as well as spectral resolution and sensitivity of telescopes in different regions of the electromagnetic spectrum. Whilst none of the 11 astrophysical diatomic molecules we investigated showed enhanced sensitive rovibronic transitions at observable intensities for astrophysical environments, we have gained a better understanding of the factors that contribute to high sensitivities. From our results, CN, CP, SiN and SiC have shown the most promise of all astrophysical diatomic molecules for further investigation, with further work currently being done on CN.

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A. Syme and L. McKemmish
Wed, 26 Aug 20
-1201/66

Comments: N/A

Experimental energy levels of 12C14N through MARVEL analysis [SSA]

http://arxiv.org/abs/2008.10809


The cyano radical (CN) is a key molecule across many different factions of astronomy and chemistry. Accurate, empirical rovibronic energy levels with uncertainties are determined for 8 doublet states of CN using the \Marvel{} (Measured Active Rotational-Vibrational Energy Levels) algorithm. \notrans{} transitions were validated from \nosources{} different published sources to generate \noenergy{} spin-rovibronic energy levels. The empirical energy levels obtained from the \Marvel{} analysis are compared to current energy levels from the \Mollist{} line list. The \Mollist{} transition frequencies are updated with \Marvel{} energy level data which brings the frequencies obtained through experimental data up to \alert{77.3\%} from the original 11.3\%, with 92.6\% of the transitions with intensities over 10$^{-23}$ cm/molecule at 1000 K now known from experimental data. At 2000 K, 100.0\% of the partition function is recovered using only \Marvel{} energy levels, while 98.2\% is still recovered at 5000 K.

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A. Syme and L. McKemmish
Wed, 26 Aug 20
-1187/66

Comments: Marvel data available here: this http URL Updated line list available: this http URL

SN Ia DDT Explosions Powered by the Zeldovich Reactivity Gradient Mechanism [SSA]

http://arxiv.org/abs/2008.05010


The aim of this work is to identify and explain the necessary conditions required for an energetic explosion of a Chandrasekhar-mass white dwarf. We construct and analyze weakly compressible turbulence models with nuclear burning effects for carbon/oxygen plasma at a density expected for deflagration-to-detonation transition (DDT) to occur. We observe formation of carbon deflagrations and transient carbon detonations at early times. As turbulence becomes increasingly inhomogeneous, sustained carbon detonations are initiated by the Zel’dovich reactivity gradient mechanism. The fuel is suitably preconditioned by the action of compressive turbulent modes with wavelength comparable to the size of resolved turbulent eddies; no acoustic wave is involved in this process. Oxygen detonations are initiated either aided by reactivity gradients or by collisions of carbon detonations. The observed evolutionary timescales are found sufficiently short for the above process to occur in the expanding, centrally ignited massive white dwarf. The inhomogeneous conditions produced prior to DDT might be of consequence for the chemical composition of the outer ejecta regions of SN Ia from the single degenerate channel, and offer potential for validation of the proposed model.

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E. Brooker, T. Plewa and D. Fenn
Thu, 13 Aug 20
-917/67

Comments: 5 pages, 4 figures, MNRAS in press

HCN production in Titan's Atmosphere: Coupling quantum chemistry and disequilibrium atmospheric modeling [EPA]

http://arxiv.org/abs/2008.04312


Hydrogen cyanide (HCN) is a critical reactive source of nitrogen for building key biomolecules relevant for the origin of life. Still, many HCN reactions remain uncharacterized by experiments and theory, and the complete picture of HCN production in planetary atmospheres is not fully understood. To improve this situation, we develop a novel technique making use of computational quantum chemistry, experimental data, and atmospheric numerical simulations. First, we use quantum chemistry simulations to explore the entire field of possible reactions for a list of primary species in N2-, CH4-, and H2-dominated atmospheres. In this process, we discover 33 new reactions with no previously known rate coefficients. From here, we develop a consistent reduced atmospheric hybrid chemical network (CRAHCN) containing experimental values when available, and our calculated rate coefficients otherwise. Next, we couple CRAHCN to a 1D chemical kinetic model (ChemKM) to compute the HCN abundance as a function of atmospheric depth on Titan. Our simulated atmospheric HCN profile agrees very well with the Cassini observations. CRAHCN contains 104 reactions however nearly all of the simulated atmospheric HCN profile can be obtained using a scaled down network of only 19 dominant reactions. From here, we form a complete picture of HCN chemistry in Titan’s atmosphere, from the dissociation of the main atmospheric species, down to the direct production of HCN along 4 major channels. One of these channels was first discovered and characterized in Pearce et al. (2019) and this work.

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B. Pearce, K. Molaverdikhani, R. Pudritz, et. al.
Wed, 12 Aug 20
-854/63

Comments: 23 pages (+41 supplementary pages), 5 figures, 5 tables (+11 supplementary tables), Accepted for publication in ApJ

Diffusive hydrogenation reactions of CO embedded in amorphous solid water at elevated temperatures ~70 K [GA]

http://arxiv.org/abs/2007.15782


The surface processes on interstellar dust grains have an important role in the chemical evolution in molecular clouds. Hydrogenation reactions on ice surfaces have been extensively investigated and are known to proceed at low temperatures mostly below 20 K. In contrast, information about the chemical processes of molecules within an ice mantle is lacking. In this work, we investigated diffusive hydrogenation reactions of carbon monoxide (CO) embedded in amorphous solid water (ASW) as a model case and discovered that the hydrogenation of CO efficiently proceeds to yield H2CO and CH3OH even above 20 K when CO is buried beneath ASW. The experimental results suggest that hydrogen atoms diffuse through the cracks of ASW and have a sufficient residence time to react with embedded CO. The hydrogenation reactions occurred even at temperatures up to ~70 K. Cracks collapse at elevated temperatures but the occurrence of hydrogenation reactions means that the cracks would not completely disappear and remain large enough for penetration by hydrogen atoms. Considering the hydrogen-atom fluence in the laboratory and molecular clouds, we suggest that the penetration of hydrogen and its reactions within the ice mantle occur in astrophysical environments. Unified Astronomy

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M. Tsuge, H. Hidaka, A. Kouchi, et. al.
Mon, 3 Aug 20
-697/58

Comments: N/A

The quest for a plausible formation route of formyl cyanide in the interstellar medium: a state-of-the-art quantum-chemical and kinetic approach [GA]

http://arxiv.org/abs/2007.08232


Interstellar complex organic molecules (iCOMs) are assumed to be mainly formed on dust-grain surfaces. However, neutral gas-phase reactions in the interstellar medium (ISM) can play an important role. In this paper, by investigating the reaction between aldehydes and the cyano radical, we show that both formaldehyde (CH$_2$O) and acetaldehyde (CH$_3$CHO) can lead to the formation of formyl cyanide (HCOCN). Owing to accurate quantum-chemical computations followed by rate constant evaluations, we have been able to suggest and validate an effective mechanism for the formation of HCOCN, one of the molecules observed in the ISM. Quite interestingly, the mechanism starting from CH$_2$O is very effective at low temperature, while that involving CH$_3$CHO becomes more efficient at temperatures above 200 K.

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F. Tonolo, J. Lupi, C. Puzzarini, et. al.
Fri, 17 Jul 20
-277/77

Comments: 13 pages, 7 figures, ApJ: accepted for publication

A twist on the reaction of the CN radical with methylamine in the interstellar medium: new hints from a state-of-the-art quantum-chemical study [CL]

http://arxiv.org/abs/2007.07657


Despite the fact that the majority of current models assume that interstellar complex organic molecules (iCOMs) are formed on dust-grain surfaces, there is some evidence that neutral gas-phase reactions play an important role. In this paper, we investigate the reaction occurring in the gas phase between methylamine (CH$_3$NH$_2$) and the cyano (CN) radical, for which only fragmentary and/or inaccurate results have been reported to date. This case study allows us to point out the pivotal importance of employing quantum-chemical calculations at the state of the art. Since the two major products of the CH$_3$NH$_2$ + CN reaction, namely the CH$_3$NH and CH$_2$NH$_2$ radicals, have not been spectroscopically characterized yet, some effort has been made for filling this gap.

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C. Puzzarini, Z. Salta, N. Tasinato, et. al.
Thu, 16 Jul 20
-228/56

Comments: 14 pages, 6 figures, MNRAS in press

MARVEL analysis of the measured high-resolution rovibronic spectra of the calcium monohydroxide radical (CaOH) [CL]

http://arxiv.org/abs/2005.14194


The calcium monohydroxide radical (CaOH) is an important astrophysical molecule relevant to cool stars and rocky exoplanets, amongst other astronomical environments. Here, we present a consistent set of highly accurate rovibronic (rotation-vibration-electronic) energy levels for the five lowest electronic states ($\tilde{X}\,^2\Sigma^+$, $\tilde{A}\,^2\Pi$, $\tilde{B}\,^2\Sigma^+$, $\tilde{C}\,^2\Delta$, $\tilde{D}\,^2\Sigma^+$) of CaOH. A comprehensive analysis of the published spectroscopic literature on this system has allowed 1955 energy levels to be determined from 3204 rovibronic experimental transitions, all with unique quantum number labelling and measurement uncertainties. The dataset covers rotational excitation up to $J=62.5$ for molecular states below 29\,000~cm$^{-1}$. The analysis was performed using the MARVEL algorithm, which is a robust procedure based on the theory of spectroscopic networks. The dataset provided will significantly aid future interstellar, circumstellar and atmospheric detections of CaOH, as well as assisting in the design of efficient laser cooling schemes in ultracold molecule research and precision tests of fundamental physics.

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Y. Wang, A. Owens, J. Tennyson, et. al.
Mon, 1 Jun 20
15/50

Comments: N/A

ExoMol line lists — XXXVIII. High-temperature molecular line list of silicon dioxide (SiO$_{\mathbf{2}}$) [EPA]

http://arxiv.org/abs/2005.13586


Silicon dioxide (SiO$_2$) is expected to occur in the atmospheres of hot rocky super-Earth exoplanets but a lack of spectroscopic data is hampering its possible detection. Here, we present the first, comprehensive molecular line list for SiO$_2$. The line list, named OYT3, covers the wavenumber range 0\,–\,6000~cm$^{-1}$ (wavelengths $\lambda > 1.67$~$\mu$m) and is suitable for temperatures up to $T=3000$~K. Almost 33 billion transitions involving 5.69 million rotation-vibration states with rotational excitation up to $J=255$ have been computed using robust first-principles methodologies. The OYT3 line list is available from the ExoMol database at this http URL

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A. Owens, E. Conway, J. Tennyson, et. al.
Fri, 29 May 20
17/75

Comments: N/A

Isomers in Interstellar Environments (I): The Case of Z- and E-Cyanomethanimine [GA]

http://arxiv.org/abs/2005.09477


In this work, we present the results of our investigation into the chemistry of Z- and E-cyanomethanimine (HNCHCN), both of which are possible precursors to the nucleobase adenine. Ab initio quantum chemical calculations for a number of reactions with atomic hydrogen were carried out. We find that the reaction H + Z/E-HNCHCN leading both to H-addition as well as H$_2$-abstraction proceed via similar short-range barriers with bimolecular rate coefficients on the order of $\sim10^{-17}$ cm$^{3}$ s$^{-1}$. These results were then incorporated into astrochemical models and used in simulations of the giant molecular cloud G+0.693. The calculated abundances obtained from these models were compared with previous observational data and found to be in good agreement, with a predicted [Z/E] ratio of $\sim3$ – somewhat smaller than the previously derived value of $6.1\pm2.4$. We find that the [Z/E] ratio in our simulations is due mostly to ion-molecule destruction rates driven by the different permanent dipoles of the two conformers. Based on these results, we propose a general rule-of-thumb for estimating the abundances of isomers in interstellar environments.

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C. Shingledecker, G. Molpeceres, V. Rivilla, et. al.
Wed, 20 May 20
36/66

Comments: The Astrophysical Journal, accepted: 17 pages, 9 figures, 7 tables

Determination of accurate rest frequencies and hyperfine structure parameters of cyanobutadiyne, HC$_5$N [IMA]

http://arxiv.org/abs/2005.09312


Very accurate transition frequencies of HC$_5$N were determined between 5.3 and 21.4 GHz with a Fourier transform microwave spectrometer. The molecules were generated by passing a mixture of HC$_3$N and C$_2$H$_2$ highly diluted in neon through a discharge valve followed by supersonic expansion into the Fabry-Perot cavity of the spectrometer. The accuracies of the data permitted us to improve the experimental $^{14}$N nuclear quadrupole coupling parameter considerably and the first experimental determination of the $^{14}$N nuclear spin-rotation parameter. The transition frequencies are also well suited to determine in astronomical observations the local speed of rest velocities in molecular clouds with high fidelity. The same setup was used to study HC$_7$N, albeit with modest improvement of the experimental $^{14}$N nuclear quadrupole coupling parameter. Quantum chemical calculations were carried out to determine $^{14}$N nuclear quadrupole and spin-rotation coupling parameters of HC$_5$N, HC$_7$N, and related molecules. These calculations included evaluation of vibrational and relativistic corrections to the non-relativistic equilibrium quadrupole coupling parameters; their considerations improved the agreement between calculated and experimental values substantially.

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T. Giesen, M. Harding, J. Gauss, et. al.
Wed, 20 May 20
61/66

Comments: 9 pages; J. Mol. Spectrosc., accepted

Chemical desorption versus energy dissipation: insights from ab-initio molecular dynamics of HCO formation [GA]

http://arxiv.org/abs/2004.11758


Molecular clouds are the cold regions of the Milky Way where stars form. They are enriched by rather complex molecules. Many of these molecules are believed to be synthesized on the icy surfaces of the interstellar submicron-sized dust grains that permeate the Galaxy. At 10 K thermal desorption is ineffcient and, therefore, why these molecules are found in the cold gas has tantalized astronomers for years. The assumption of the current models, called chemical desorption, is that the molecule formation energy released by the chemical reaction at the grain surface is partially absorbed by the grain and the remaining one causes the ejection of the newly formed molecule into the gas. Here we report an accurate ab-initio molecular dynamics simulations aimed to study the fate of the energy released by the first reaction of the H addition chain on CO, CO + H $\rightarrow$ HCO, occurring on a crystalline ice surface model. We show that about 90% of the HCO formation energy is injected towards the ice in the first picosecond, leaving HCO with an energy content (10-15 kJ mol$^{-1}$) more than a factor two lower than its adsorption energy (30 kJ mol$^{-1}$). As a result, in agreement with laboratory experiments, we conclude that chemical desorption is ineffcient for this specific system, namely H + CO on crystalline ice. We suspect this behavior to be quite general when dealing with hydrogen bonds, which are responsible of both the cohesive energy of the ice mantle and the interaction with adsorbates, as the HCO radical, even though ad hoc simulations are needed to draw specific conclusions on other systems.

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S. Pantaleone, J. Enrique-Romero, C. Ceccarelli, et. al.
Mon, 27 Apr 20
29/45

Comments: Appendix not included. Submitted to ApJ

Hemolithin: a Meteoritic Protein containing Iron and Lithium [EPA]

http://arxiv.org/abs/2002.11688


This paper characterizes the first protein to be discovered in a meteorite. Amino acid polymers previously observed in Acfer 086 and Allende meteorites [1,2] have been further characterized in Acfer 086 via high precision MALDI mass spectrometry to reveal a principal unified structure of molecular weight 2320 Daltons that involves chains of glycine and hydroxy-glycine residues terminated by iron atoms, with additional oxygen and lithium atoms. Signal-to-noise ratios up to 135 have allowed the quantification of iron and lithium in the various MALDI fragments via the isotope satellites due to their respective minority isotopic masses 54Fe and 6Li. Analysis of the complete spectrum of isotopes associated with each molecular fragment shows 2H enhancements above terrestrial averaging 25,700 parts per thousand (sigma = 3,500, n=15), confirming extra-terrestrial origin and hence the existence of this molecule within the asteroid parent body of the CV3 meteorite class. The molecule is tipped by an iron-oxygen-iron grouping that in other terrestrial contexts has been proposed to be capable of absorbing photons and splitting water into hydroxyl and hydrogen moieties.

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M. McGeoch, S. Dikler and J. McGeoch
Thu, 27 Feb 20
23/51

Comments: 33 pages including 14 figures, 10 tables

Spectroscopy of YO from first principles [CL]

http://arxiv.org/abs/2002.09994


We report an ab initio study on the spectroscopy of the open-shell diatomic molecule yttrium oxide, YO. The study considers the six lowest doublet states, $X\,{}^{2}\Sigma^{+}$, $A\,{}^{2}\Pi$, $C\,{}^{2}\Pi$, $A’\,{}^{2}\Delta$, $B\,{}^{2}\Sigma^{+}$, $D\,{}^{2}\Sigma^{+}$ and a few higher-lying quartet states using high levels of electronic structure theory and accurate nuclear motion calculations. The coupled cluster singles, doubles, and perturbative triples, CCSD(T), and multireference configuration interaction (MRCI) methods are employed in conjunction with a relativistic pseudopotential on the yttrium atom and a series of correlation-consistent basis sets ranging in size from triple-$\zeta$ to quintuple-$\zeta$ quality. Core-valence correlation effects are taken into account and complete basis set limit extrapolation is performed for CCSD(T). Spin-orbit coupling is included through the use of both MRCI state-interaction with spin-orbit (SI-SO) approach and four-component relativistic equation-of-motion CCSD calculations. Using the ab initio data for bond lengths ranging from 1.0 to 2.5 A, we compute 6 potential energy, 12 spin-orbit, 8 electronic angular momentum, 6 electric dipole moment and 12 transition dipole moment (4 parallel and 8 perpendicular) curves which provide a complete description of the spectroscopy of the system of six lowest doublet states. The Duo nuclear motion program is used to solve the coupled nuclear motion Schr\”{o}dinger equation for these six electronic states. The spectra of $^{89}$Y$^{16}$O simulated for different temperatures are compared with several available high resolution experimental studies; good agreement is found once minor adjustments are made to the electronic excitation energies.

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A. Smirnov, V. Solomonik, S. Yurchenko, et. al.
Tue, 25 Feb 20
48/76

Comments: N/A

Cavity ring-down spectroscopy of CO$_2$ near $λ$ = 2.06 $μ$m: Accurate transition intensities for the Orbiting Carbon Observatory-2 (OCO-2) "strong band" [CL]

http://arxiv.org/abs/2002.09584


The $\lambda$ = 2.06 $\mu$m absorption band of $^{12}$C$^{16}$O$_2$ is widely used for the remote sensing of atmospheric carbon dioxide, making it relevant to many important top-down measurements of carbon flux. The forward models used in the retrieval algorithms employed in these measurements require increasingly accurate line intensity and line shape data from which absorption cross-sections can be computed. To overcome accuracy limitations of existing line lists, we used frequency-stabilized cavity ring-down spectroscopy to measure 39 transitions in the $^{12}$C$^{16}$O$_2$ absorption band. We estimate the relative combined standard uncertainty for the measured intensities to be $u_r$ = 0.09 %, which is dominated by several type B (systematic) contributions each with $u_r$ = 0.04 %. We predicted the $J$-dependence of the measured intensities using two theoretical models: a one-dimensional quantum mechanical model with Herman-Wallis rotation-vibration corrections, and a line-by-line ab initio model [Zak et al. JQSRT 2016;177:31-42]. For the second approach, we fit only a single factor to rescale the theoretical integrated band intensity to be consistent with the measured intensities. We find that the latter approach yields an equally adequate representation of the fitted $J$-dependent intensity data and provides the most physically general representation of the results. Our recommended value for the integrated band intensity equal to 7.180$\times$10$^{-21}$ cm molecule$^{-1}$ $\pm$ 6$\times$10$^{-24}$ cm molecule$^{-1}$ is based on the rescaled ab initio model and corresponds to a fitted scale factor of 1.0065 $\pm$ 0.0002. Comparisons of literature intensity values to our results reveal systematic deviations ranging from $-$1.1 % to 0.4 %.

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H. Fleurbaey, H. Yi, E. Adkins, et. al.
Tue, 25 Feb 20
66/76

Comments: 30 pages, 9 figures, 4 tables

A Theoretical Investigation of the Possible Detection of C24 in Space [GA]

http://arxiv.org/abs/2002.08960


Astronomical infrared spectral features at ~6.6, 9.8 and 20 micronm have recently been suggested as being due to the planar graphene form of C24 carbon cluster. Here we report density functional theory and coupled cluster calculations on wavefunctions stability, relative energies, and infrared spectra of four different types of C24 isomers, including the graphene and fullerene forms. The types of vibrational motions under these bands are also discussed. Among the four isomers, we find that the astronomical data are best approximated by the graphene form of C24.

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S. Sadjadi, S. Kwok, F. Cataldo, et. al.
Mon, 24 Feb 20
28/49

Comments: 15 pages, 4 figures

Empirical Line Lists in the ExoMol Database [SSA]

http://arxiv.org/abs/2002.06939


The ExoMol database aims to provide comprehensive molecular line lists for exoplanetary and other hot atmospheres. The data are expanded by inclusion of empirically derived line lists taken from the literature for a series of diatomic molecules, namely CH, NH, OH, AlCl, AlF, OH$^+$, CaF, MgF, KF, NaF, LiCl, LiF, MgH, TiH, CrH, FeH, C$_2$, CP, CN, CaH, and triplet N$_2$. Generally, these line lists are constructed from measured spectra using a combination of effective rotational Hamiltonian models for the line positions and ab initio (transition) dipole moments to provide intensities. This work results in the inclusion of 22 new molecules (36 new isotopologues) in the ExoMol database.

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Y. Wang, J. Tennyson and S. Yurchenko
Tue, 18 Feb 20
47/72

Comments: N/A

Revisiting the reactivity between HCO and CH$_3$ on interstellar grain surfaces [GA]

http://arxiv.org/abs/2002.06101


Formation of interstellar complex organic molecules is currently thought to be dominated by the barrierless coupling between radicals on the interstellar icy grain surfaces. Previous standard DFT results on the reactivity between CH$_3$ and HCO on amorphous water surfaces, showed that formation of CH$_4$ + CO by H transfer from HCO to CH$_3$ assisted by water molecules of the ice was the dominant channel. However, the adopted description of the electronic structure of the biradical (i.e., CH$_3$/HCO) system was inadequate (without the broken-symmetry (BS) approach). In this work, we revisit the original results by means of BS-DFT both in gas phase and with one water molecule simulating the role of the ice. Results indicate that adoption of BS-DFT is mandatory to describe properly biradical systems. In the presence of the single water molecule, the water-assisted H transfer exhibits a high energy barrier. In contrast, CH$_3$CHO formation is found to be barrierless. However, direct H transfer from HCO to CH$_3$ to give CO and CH$_4$ presents a very low energy barrier, hence being a potential competitive channel to the radical coupling and indicating, moreover, that the physical insights ofthe original work remain valid.

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J. Enrique-Romero, S. Álvarez-Barcia, F. Kolb, et. al.
Mon, 17 Feb 20
28/53

Comments: Submitted to MNRAS main journal. For associated supporting material refer to the publication in MNRAS. Accepted 2020 February 14. Received 2020 February 14

The effect of CO-H2O collisions in the rotational excitation of cometary CO [EPA]

http://arxiv.org/abs/2001.09562


We present the first accurate rate coefficients for the rotational excitation of CO by H2O in the kinetic temperature range 5-100 K. The statistical adiabatic channel method (SACM) is combined with a high-level rigid-rotor CO-H2O intermolecular potential surface. Transitions among the first 11 rotational levels of CO and the first 8 rotational levels of both para-H2O and ortho-H2O are considered. Our rate coefficients are compared to previous data from the literature and they are also incorporated in a simple non-LTE model of cometary coma including collision-induced transitions, solar radiative pumping and radiative decay. We find that the uncertainties in the collision data have significant influence on the CO population distribution for H2O densities in the range 10^3-10^8 cm^-3. We also show that the rotational distribution of H2O plays an important role in CO excitation (owing to correlated energy transfer in both CO and H2O), while the impact of the ortho-to-para ratio of H2O is found to be negligible.

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A. Faure, F. Lique and J. Loreau
Tue, 28 Jan 20
22/63

Comments: 8 pages, 7 figures, accepted for publication in MNRAS (January 20 2020)

Photolysis-induced scrambling of PAHs as a mechanism for deuterium storage [SSA]

http://arxiv.org/abs/2001.09835


Aim. We investigate the role of PAHs as a sink for deuterium in the interstellar medium and study UV photolysis as a potential process in the variations of the deuterium fractionation in the ISM. Methods. The UV photo-induced fragmentation of various isotopologues of D-enriched, protonated anthracene and phenanthrene ions was recorded in a FTICR mass spectrometer. IRMPD spectroscopy using FELIX provided the IR spectra that were compared to DFT vibrational spectra; reaction barriers and rates were also calculated and related to the product abundances. Results. The mass spectra for both UV and IRMPD photolysis show the loss of H from [D-C${14}$H${10}$]$^+$, whereas [H-C${14}$D${10}$]$^+$ shows a strong preference for D loss. Calculations reveal facile 1,2-H and -D shift reactions, with barriers lower than the energy supplied by the photo-excitation process. Together with confirmation of the ground-state structures via the IR spectra, we determined that the photolytic processes in the 2 PAHs are largely governed by scrambling where the H and the D atoms relocate between different peripheral C atoms. The $\sim$0.1 eV difference in zero-point energy between C-H and C-D bonds ultimately leads to faster H scrambling than D scrambling, and increased H atom loss compared to D. Conclusion. Scrambling is common in PAH cations under UV radiation. Upon photoexcitation of deuterium-enriched PAHs, the scrambling results in a higher probability for the aliphatic D atom to migrate to an aromatic site, protecting it from elimination. This could lead to increased deuteration as a PAH moves towards more exposed interstellar environments. Also, large, compact PAHs with an aliphatic C-HD group on solo sites might be responsible for the majority of aliphatic C-D stretching bands seen in astronomical spectra.

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S. Wiersma, A. Candian, J. Bakker, et. al.
Tue, 28 Jan 20
35/63

Comments: 13 pages, 5 figures. Abstract abridged to meet ArXiv size limit. Accepted for publications in A&A

Diatomic rovibronic transitions as potential probes for proton-to-electron mass ratio across cosmological time [CL]

http://arxiv.org/abs/2001.06121


Astrophysical molecular spectroscopy is an important method of searching for new physics through probing the variation of the proton-to-electron mass ratio, $\mu$, with existing constraints limiting variation to a fractional change of less than 10$^{-17}$/year. To improve on this constraint and therefore provide better guidance to theories of new physics, new molecular probes will be useful. These probes must have spectral transitions that are observable astrophysically and have different sensitivities to variation in the proton-to-electron mass ratio. Here, we concisely detail how astrophysical observations constrain the set of potential molecular probes and promising sensitive transitions based on how the frequency and intensity of these transitions align with available telescopes and observational constraints. Our detailed investigation focuses on rovibronic transitions in astrophysical diatomic molecules, using the spectroscopic models of 11 diatomics to identify sensitive transitions and probe how they generally arise in real complex molecules with many electronic states and fine structure. While none of the 11 diatomics investigated have sensitive transitions likely to be astrophysically observable, we have found that at high temperatures (1000 K) five of these diatomics have a significant number of low intensity sensitive transitions arising from an accidental near-degeneracy between vibrational levels in the ground and excited electronic state. This insight enables screening of all astrophysical diatomics as potential probes of proton-to-electron mass variation, with CN, CP, SiN and SiC being the most promising candidates for further investigation for sensitivity in rovibronic transitions.

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A. Syme, A. Mousley, M. Cunningham, et. al.
Mon, 20 Jan 20
53/60

Comments: N/A

Diatomic rovibronic transitions as potential probes for proton-to-electron mass ratio across cosmological time [CL]

http://arxiv.org/abs/2001.06121


Astrophysical molecular spectroscopy is an important method of searching for new physics through probing the variation of the proton-to-electron mass ratio, $\mu$, with existing constraints limiting variation to a fractional change of less than 10$^{-17}$/year. To improve on this constraint and therefore provide better guidance to theories of new physics, new molecular probes will be useful. These probes must have spectral transitions that are observable astrophysically and have different sensitivities to variation in the proton-to-electron mass ratio. Here, we concisely detail how astrophysical observations constrain the set of potential molecular probes and promising sensitive transitions based on how the frequency and intensity of these transitions align with available telescopes and observational constraints. Our detailed investigation focuses on rovibronic transitions in astrophysical diatomic molecules, using the spectroscopic models of 11 diatomics to identify sensitive transitions and probe how they generally arise in real complex molecules with many electronic states and fine structure. While none of the 11 diatomics investigated have sensitive transitions likely to be astrophysically observable, we have found that at high temperatures (1000 K) five of these diatomics have a significant number of low intensity sensitive transitions arising from an accidental near-degeneracy between vibrational levels in the ground and excited electronic state. This insight enables screening of all astrophysical diatomics as potential probes of proton-to-electron mass variation, with CN, CP, SiN and SiC being the most promising candidates for further investigation for sensitivity in rovibronic transitions.

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A. Syme, A. Mousley, M. Cunningham, et. al.
Mon, 20 Jan 20
43/60

Comments: N/A

Anionic hydrogen clusters as a source of diffuse interstellar bands (DIBs) [GA]

http://arxiv.org/abs/1912.11605


The sources behind numerous key diffuse interstellar bands (DIBs) remain elusive, and thus evidence is presented here that a family of seven anionic hydrogen atomic clusters (H(-)2n+1, n = 1 to 7) are pertinent contributors. Configuration interaction calculations show hat these charge-induced dipole clusters are stable at temperatures characteristic of the interstellar medium, and emerge from the most abundant element in the Universe. The clusters’ spectra yield 25 absorption optical lines that align with observed DIBs to within the computational uncertainties. The absorption bands are due to excitations from the ground states of the clusters to metastable states.

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L. Huang, C. Matta, D. Majaess, et. al.
Mon, 30 Dec 19
8/51

Comments: 20 pages in total including 3 figures, 3 tables, and Supporting Information

Anionic hydrogen clusters as a source of diffuse interstellar bands (DIBs) [GA]

http://arxiv.org/abs/1912.11605


The sources behind numerous key diffuse interstellar bands (DIBs) remain elusive, and thus evidence is presented here that a family of seven anionic hydrogen atomic clusters (H(-)2n+1, n = 1 to 7) are pertinent contributors. Configuration interaction calculations show hat these charge-induced dipole clusters are stable at temperatures characteristic of the interstellar medium, and emerge from the most abundant element in the Universe. The clusters’ spectra yield 25 absorption optical lines that align with observed DIBs to within the computational uncertainties. The absorption bands are due to excitations from the ground states of the clusters to metastable states.

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L. Huang, C. Matta, D. Majaess, et. al.
Mon, 30 Dec 19
32/51

Comments: 20 pages in total including 3 figures, 3 tables, and Supporting Information

High-resolution gas phase spectroscopy of molecules desorbed from an ice surface: a proof-of-principle study [IMA]

http://arxiv.org/abs/1912.09839


High-resolution gas phase spectroscopy techniques in the microwave, millimeter-wave and terahertz spectral ranges can be used to study complex organic molecules desorbed from interstellar ice analogues surface with a high sensitivity. High-resolution gas phase spectroscopy gives unambiguous information about the molecular composition, the molecular structure, and transition frequencies needed for their detection by radio telescopes in various interstellar and circumstellar environments. The results will be useful not only for interpreting astronomical spectra and understanding astrophysical processes, but also for more general studies of gas-surface chemistry. This paper presents a new experimental approach based on a combination of a chirped-pulse Fourier transform microwave spectrometer detection and a low temperature surface desorption experiment. The experimental set-up is benchmarked on the desorption of ammonia ice detected by high-resolution gas phase microwave spectroscopy.

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P. Theulé, C. Endres, M. Hermanns, et. al.
Mon, 23 Dec 19
10/50

Comments: accepted on Earth Space and Chemistry

Fragmentation and isomerization of polycyclic aromatic hydrocarbons in the interstellar medium: coronene as a case study [GA]

http://arxiv.org/abs/1912.08426


Aims. Due to the limitations of current computational technology, the fragmentation and isomerization products of vibrationally-excited polycyclic aromatic hydrocarbon (PAH) molecules and their derivatives are poorly studied. In this work, we investigate the intermediate products of PAHs and their derivatives as well as the gas-phase reactions relevant to the interstellar medium, with coronene as a case study.
Methods. Based on the semi-empirical method of PM3 as implemented in the CP2K program, molecular dynamics simulations are performed to model the major processes (e.g., vibrations, fragmentations, and isomerizations) of coronene and its derivatives (e.g., methylated coronene, hydrogenated coronene, dehydrogenated coronene, nitrogen-substituted coronene, and oxygen-substituted coronene) at temperatures of 3000 K and 4000 K.
Results. We find that the anharmonic effects are crucial for the simulation of vibrational excitation. For the molecules studied here, H2, CO, HCN, and CH2 are the major fragments. Following the dissociation of these small units, most of the molecules could maintain their ring structures, but a few molecules would break completely into carbon chains. The transformation from hexagon to pentagon or heptagon may occur and the heteroatomic substitutions (e.g., N- or O-substitutions) facilitate the transformation.

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T. Chen, Y. Luo and A. Li
Thu, 19 Dec 19
35/82

Comments: 9 pages, 10 figures; accepted for publication in A&A

Spectroscopy of corannulene cations in helium nanodroplets [CL]

http://arxiv.org/abs/1912.08692


Helium tagging in action spectroscopy is an efficient method for measuring the absorption spectrum of complex molecular ions with minimal perturbations to the gas phase spectrum. We have used superfluid helium nanodroplets doped with corannulene to prepare cations of these molecules complexed with different numbers of He atoms. In total we identify 13 different absorption bands from corannulene cations between 5500 {\AA} and 6000 {\AA}. The He atoms cause a small, chemically induced redshift to the band positions of the corannulene ion. By studying this effect as a function of the number of solvating atoms we are able to identify the formation of solvation structures that are not visible in the mass spectrum. The solvation features detected with the action spectroscopy agree very well with the results of atomistic modeling based on path-integral molecular dynamics simulations. By additionally doping our He droplets with D$_2$, we produce protonated corannulene ions. The absorption spectrum of these ions differs significantly from the case of the radical cations as the numerous narrow bands are replaced by a broad absorption feature that spans nearly 2000 {\AA} in width.

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M. Gatchell, P. Martini, F. Laimer, et. al.
Thu, 19 Dec 19
37/82

Comments: 10 pages, 7 figures, published in Faraday Discuissions

Measurements and semi-empirical calculations of CO2+CH4 and CO2+H2 collision-induced absorptions across a wide range of wavenumbers and temperatures. Application for the prediction of early Mars surface temperature [EPA]

http://arxiv.org/abs/1912.05630


Reducing atmospheres have recently emerged as a promising scenario to warm the surface of early Mars enough to drive the formation of valley networks and other ancient aqueous features that have been detected so far on the surface of Mars. Here we present a series of experiments and calculations to better constrain CO2+CH4 and CO2+H2 collision-induced absorptions (CIAs) as well as their effect on the prediction of early Mars surface temperature. First, we carried out a new set of experimental measurements (using the AILES line of the SOLEIL synchrotron) of both CO2+CH4 and CO2+H2 CIAs. These measurements confirm the previous results of Turbet et al. 2019, Icarus vol. 321, while significantly reducing the experimental uncertainties. Secondly, we fitted a semi-empirical model to these CIAs measurements, allowing us to compute the CO2+CH4 and CO2+H2 CIAs across a broad spectral domain (0-1500cm-1) and for a wide range of temperatures (100-600K). Last, we performed 1-D numerical radiative-convective climate calculations (using the LMD Generic Model) to compute the surface temperature expected on the surface of early Mars for several CO2, CH4 and H2 atmospheric contents, taking into account the radiative effect of these revised CIAs. These calculations demonstrate that thick CO2+H2-dominated atmospheres remain a viable solution for warming the surface of Mars above the melting point of water, but not CO2+CH4-dominated atmospheres. Our calculated CO2+CH4 and CO2+H2 CIA spectra and predicted early Mars surface temperatures are provided to the community for future uses.

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M. Turbet, C. Boulet and T. Karman
Fri, 13 Dec 19
73/75

Comments: Submitted for publication to Icarus. CO2+H2 and CO2+CH4 CIAs calculated tables (HITRAN format) – as well as predicted early Mars surface temperatures – are available on demand

Photo-processing of astro-PAHs [GA]

http://arxiv.org/abs/1912.03137


Polycyclic aromatic hydrocarbons (PAHs) are key species in astrophysical environments in which vacuum ultraviolet (VUV) photons are present, such as star-forming regions. The interaction with these VUV photons governs the physical and chemical evolution of PAHs. Models show that only large species can survive. However, the actual molecular properties of large PAHs are poorly characterized and the ones included in models are only an extrapolation of the properties of small and medium-sized species. We discuss here experiments performed on trapped ions including some at the SOLEIL VUV beam line DESIRS. We focus on the case of the large dicoronylene cation, C48H20+ , and compare its behavior under VUV processing with that of smaller species. We suggest that C2H2 is not a relevant channel in the fragmentation of large PAHs. Ionization is found to largely dominate fragmentation. In addition, we report evidence for a hydrogen dissociation channel through excited electronic states. Although this channel is minor, it is already effective below 13.6 eV and can significantly influence the stability of astro-PAHs. We emphasize that the competition between ionization and dissociation in large PAHs should be further evaluated for their use in astrophysical models.

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C. Joblin, G. Wenzel, S. Castillo, et. al.
Mon, 9 Dec 19
15/53

Comments: N/A

Molecular Simulations for the Spectroscopic Detection of Atmospheric Gases [CL]

http://arxiv.org/abs/1911.04238


Unambiguously identifying molecules in spectra is of fundamental importance for a variety of scientific and industrial uses. Interpreting atmospheric spectra for the remote detection of volatile compounds requires information about the spectrum of each relevant molecule. However, spectral data currently exist for a few hundred molecules and only a fraction of those have complete spectra (e.g. H$_2$O, NH$_3$). Consequently, molecular detections in atmospheric spectra remain vulnerable to false positives, false negatives, and missassignments. There is a key need for spectral data for a broad range of molecules. Given how challenging it is to obtain high-resolution molecular spectra, there is great value in creating intermediate approximate spectra that can provide a starting point for the analysis of atmospheric spectra.
Using a combination of experimental measurements, organic chemistry, and quantum mechanics, RASCALL (Rapid Approximate Spectral Calculations for ALL) is a computational approach that provides approximate spectral data for any given molecule, including thousands of potential atmospheric gases, in seconds. RASCALL 1.0 simulates molecular spectra by interpreting functional group data from experimental and theoretical sources to estimate the position and strength of molecular bands. The RASCALL 1.0 spectra consist of approximate band centers and qualitative intensities. RASCALL can also be used to study spectral patterns between molecules, and to highlight ambiguities in molecular detections. The RASCALL catalogue, and its preliminary version RASCALL 1.0, contains spectral data for more molecules than any other publicly available database, with applications in all fields interested in the detection of molecules in the gas phase. The preliminary catalogue of molecular data and associated documentation are freely available online and will be routinely updated.

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C. Sousa-Silva, J. Petkowski and S. Seager
Tue, 12 Nov 19
79/84

Comments: N/A

Efficient Production of S$_8$ in Interstellar Ices: The effects of cosmic ray-driven radiation chemistry and non-diffusive bulk reactions [GA]

http://arxiv.org/abs/1911.01239


In this work, we reexamine sulfur chemistry occurring on and in the ice mantles of interstellar dust grains, and report the effects of two new modifications to standard astrochemical models; namely, (a) the incorporation of cosmic ray-driven radiation chemistry and (b) the assumption of fast, non-diffusive reactions for key radicals in the bulk. Results from our models of dense molecular clouds show that these changes can have a profound influence on the abundances of sulfur-bearing species in ice mantles, including a reduction in the abundance of solid-phase H$_2$S and HS, and a significant increase in the abundances of OCS, SO$_2$, as well as pure allotropes of sulfur, especially S$_8$. These pure-sulfur species – though nearly impossible to observe directly – have long been speculated to be potential sulfur reservoirs and our results represent possibly the most accurate estimates yet of their abundances in the dense ISM. Moreover, the results of these updated models are found to be in good agreement with available observational data. Finally, we examine the implications of our findings with regard to the as-yet-unknown sulfur reservoir thought to exist in dense interstellar environments.

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C. Shingledecker, T. Lamberts, J. Laas, et. al.
Tue, 5 Nov 19
23/72

Comments: ApJ, accepted: 37 pages, 8 figures

Chemistry on rotating grain surfaces: ro-thermal hopping and segregation of molecules in ice mantles [GA]

http://arxiv.org/abs/1910.12205


Grain surfaces play a central role in the formation and desorption of molecules in space. To form molecules on a grain surface, adsorbed species trapped in binding sites must be mobile and migrate to adjacent sites. Thermal hopping is a popular mechanism for the migration of adsorbed species when the grain surface is warmed up by stellar radiation. However, previous studies disregarded the fact that grains can be spun-up to suprathermal rotation by radiative torques (RATs) during grain heating process. To achieve an accurate model of surface astrochemistry, in this paper, we study the effect of grain suprathermal rotation by RATs on thermal hopping of adsorbed species on icy grain mantles. We find that centrifugal force due to grain suprathermal rotation can increase the mobility of radicals on/in the ice mantle compared to the prediction by thermal hopping, and we term this mechanism ro-thermal hopping. The rate of ro-thermal hopping depends both on the local radiation energy density (i.e., grain temperature) and gas density, whereas thermal hopping only depends on grain temperature. We calculate the decrease in grain temperature required by ro-thermal hopping to produce the same hopping rate as thermal hopping and find that it increases with increasing the diffusion energy and decreasing the gas density. We finally study the effect of grain suprathermal rotation on the segregation of ice mixtures and find that ro-thermal segregation of CO$_2$ from H$_2$O-CO$_2$ ices can occur at much lower temperatures than thermal segregation reported by experiments. Our results indicate that grain suprathermal rotation can enhance mobility, formation, desorption, and segregation of molecules in icy grain mantles.

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T. Hoang
Tue, 29 Oct 19
52/78

Comments: 13 pages, 8 figures, to be submitted; comments are welcome

Effect of the isotropic collisions with neutral hydrogen on the polarization of the CN solar molecule [SSA]

http://arxiv.org/abs/1910.10058


Our work is concerned with the case of the solar molecule CN which presents conspicuous profiles of scattering polarization. We start by calculating accurate PES for the singlet and triplet electronic ground states in order to characterize the collisions between the CN molecule in its $X \; ^2\Sigma$ state and the hydrogen in its ground state $^2S$. The PES are included in the Schr\”oodinger equation to obtain the scattering matrix and the probabilities of collisions. Depolarizing collisional rate coefficients are computed in the framework of the infinite order sudden approximation for temperatures ranging from $T= 2000$ K to $T= 15000$ K. Interpretation of the results and comparison between singlet and triplet collisional rate coefficients are detailed. We show that, for typical photospheric hydrogen density ($n_{H} = 10^{15}-10^{16}$ cm$^{-3}$), the $X \; ^2\Sigma$ state of CN is partially or completely depolarized by isotropic collisions.

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S. Qutub, M. Derouich, Y. Kalugina, et. al.
Wed, 23 Oct 19
62/64

Comments: Accepted for publication in MNRAS (Accepted October 22, 2019). 23 pages, 3 tables, 13 figures

The infrared bands of polycyclic aromatic hydrocarbons in the 1.6-1.7 μm wavelength region [IMA]

http://arxiv.org/abs/1910.07062


Context. The 3.3 $\mu$m aromatic C-H stretching band of polycyclic aromatic hydrocarbon (PAH) molecules seen in a wide variety of astrophysical regions is often accompanied by a series of weak satellite bands at ~3.4-3.6 $\mu$m. One of these sources, IRAS 21282+5050, a planetary nebula, also exhibits a weak band at ~1.68 $\mu$m. While the satellite features at ~3.4-3.6 $\mu$m are often attributed to the anharmonicities of PAHs, it is not clear whether overtones or combination bands dominate the 1.68 $\mu$m feature.
Aims. In this work, we examine the anharmonic spectra of eight PAH molecules, including anthracene, tetracene, pentacene, phenanthrene, chrysene, benz[a]anthracene, pyrene, and perylene, to explore the origin of the infrared bands in the 1.6-1.7 $\mu$m waveelngth region.
Methods. Density Functional Theory (DFT) in combination with the vibrational second-order perturbation theory (VPT2) is utilized for computing the anharmonic spectra of PAHs. To simulate the vibrational excitation process of PAHs, the Wang-Landau random walk technique is employed.
Results. All the dominant bands in the 1.6-1.7 $\mu$m wavelength range and in the 3.1-3.5 $\mu$m C-H stretching region are calculated and tabulated. It is demonstrated that combination bands dominate the 1.6-1.7 $\mu$m region, while overtones are rare and weak in this region. We also calculate the intensity ratios of the 3.1-3.5 $\mu$m C-H stretching features to the bands in the 1.6-1.7 $\mu$m region, $I_{3.1-3.5}/I_{1.6-1.7}$, for both ground and vibrationally excited states. On average, we obtain $\langle I_{3.1-3.5}/I_{1.6-1.7} \rangle$ $\approx$ 12.6 and $\langle I_{3.1-3.5}/I_{1.6-1.7} \rangle$ $\approx$ 17.6 for PAHs at ground states and at vibrationally excited states, respectively.

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T. Chen, Y. Luo and A. Li
Thu, 17 Oct 19
1/62

Comments: N/A

The infrared spectrum of protonated buckminsterfullerene, C60H+ [CL]

http://arxiv.org/abs/1910.04533


Although fullerenes have long been hypothesized to occur in interstellar environments, their actual unambiguous spectroscopic identification is of more recent date. C60, C70 and C60+ now constitute the largest molecular species individually identified in the interstellar medium (ISM). Fullerenes have significant proton affinities and it was suggested that C60H+ is likely the most abundant interstellar analogue of C60. We present here the first laboratory infrared (IR) spectrum of gaseous C60H+. Symmetry breaking relative to C60 produces an IR spectrum that is much richer than that of C60. The experimental spectrum is used to benchmark theoretical spectra indicating that the B3LYP density functional with the 6-311+G(d,p) basis set accurately reproduces the spectrum. Comparison with IR emission spectra from two planetary nebulae, SMP LMC56 and SMC16, that have been associated with high C60 abundances, indicate that C60H+ is a plausible contributor to their IR emission.

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J. Palotás, J. Martens, G. Berden, et. al.
Mon, 14 Oct 19
12/69

Comments: 9 pages, 4 figures

Investigations into the rotational spectrum of isotopic methyl mercaptan, (13)CH3SH, in the laboratory and towards Sagittarius B2(N2) [SSA]

http://arxiv.org/abs/1910.02259


Methyl mercaptan (CH3SH) is a known interstellar molecule with abundances high enough that the detection of some of its minor isotopologues is promising. The present study aims at providing accurate spectroscopic parameters for the (13)CH3SH isotopologue to facilitate searches in the interstellar medium at millimetre and submillimetre wavelengths. Through careful analysis of recent CH3SH spectra from 49-510 GHz and 1.1-1.5 THz recorded at natural isotopic composition, extensive assignments were possible not only for the ground torsional state of (13)CH3SH, but also in the first and second excited states. The torsion-rotation spectrum displays complex structure due to the large-amplitude internal rotation of the (13)CH3 group, similar to the main and other minor isotopic species of methyl mercaptan. The assigned transition frequencies have been fitted to within experimental error with a 52-parameter model employing the RAM36 programme. With predictions based on this fit, (13)CH3SH was searched for in spectra from the Atacama Large Millimetre/submillimetre Array (ALMA) towards the Galactic centre source Sgr B2(N2). Several transitions were expected to be observable, but all of them turned out to be severely blended with emission from other species, which prevents us from identifying (13)CH3SH in this source.

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V. Ilyushin, O. Zakharenko, F. Lewen, et. al.
Tue, 8 Oct 19
44/88

Comments: 20 pages (with figures and tables); Can. J. Phys. (this https URL), accepted

Synthesizing carbon nanotubes in space [IMA]

http://arxiv.org/abs/1909.09182


Context. As the 4th most abundant element in the universe, carbon (C) is widespread in the interstellar medium (ISM) in various allotropic forms (e.g., fullerenes have been identified unambiguously in many astronomical environments, the presence of polycyclic aromatic hydrocarbon molecules in space has been commonly admitted, and presolar graphite as well as nanodiamonds have been identified in meteorites). As stable allotropes of these species, whether carbon nanotubes (CNTs) and their hydrogenated counterparts are also present in the ISM or not is unknown.
Aims. We explore the possible routes for the formation of CNTs in the ISM and calculate their fingerprint vibrational spectral features in the infrared (IR).
Methods. We study the hydrogen-abstraction/acetylene-addition (HACA) mechanism and investigate the synthesis of nanotubes using density functional theory (DFT). The IR vibrational spectra of CNTs and hydrogenated nanotubes (HNTs), as well as their cations, have also been obtained with DFT.
Results. We find that CNTs could be synthesized in space through a feasible formation pathway. CNTs and cationic CNTs, as well as their hydrogenated counterparts, exhibit intense vibrational transitions in the IR. Their possible presence in the ISM could be investigated by comparing the calculated vibrational spectra with astronomical observations made by the Infrared Space Observatory, Spitzer Space Telescope, and particularly the upcoming James Webb Space Telescope.

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T. Chen and A. Li
Mon, 23 Sep 19
42/46

Comments: N/A

Ultraslow radiative cooling of C$_n^-$ ($n=3-5$) [CL]

http://arxiv.org/abs/1909.07087


Ultraslow radiative cooling lifetimes and adiabatic detachment energies for three astrochemically relevant anions, C$_n^-$ ($n=3-5$), are measured using the Double ElectroStatic Ion Ring ExpEriment (DESIREE) infrastructure at Stockholm University. DESIREE maintains a background pressure of $\approx$10$^{-14}$\,mbar and temperature of $\approx$13\,K, allowing storage of mass-selected ions for hours and providing conditions coined a “molecular cloud in a box”. Here, we construct two-dimensional (2D) photodetachment spectra for the target anions by recording photodetachment signal as a function of irradiation wavelength and ion storage time (seconds to minute timescale). Ion cooling lifetimes, which are associated with infrared radiative emission, are extracted from the 2D photodetachment spectrum for each ion by tracking the disappearance of vibrational hot-band signal with ion storage time, giving $\frac{1}{e}$ cooling lifetimes of 3.1$\pm$0.1\,s (C$_3^-$), 6.8$\pm$0.5\,s (C$_4^-$) and 24$\pm$5\,s (C$_5^-$). Fits of the photodetachment spectra for cold ions, i.e. those stored for at least 30\,s, provides adiabatic detachment energies in good agreement with values from laser photoelectron spectroscopy. Ion cooling lifetimes are simulated using a Simple Harmonic Cascade model, finding good agreement with experiment and providing a mode-by-mode understanding of the radiative cooling properties. The 2D photodetachment strategy and radiative cooling modeling developed in this study could be applied to investigate the ultraslow cooling dynamics of wide range of molecular anions.

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J. Bull, M. Scholz, E. Carrascosa, et. al.
Tue, 17 Sep 19
19/98

Comments: N/A

Threshold dissociation of the 1-ethynylpyrene cation at internal energies relevant to H I regions [GA]

http://arxiv.org/abs/1909.05718


Photoelectron photoion coincidence spectroscopy has been used to measure the threshold photoelectron spectrum of 1-ethynylpyrene and to obtain the breakdown graph describing the dissociation of the 1-ethynylpyrene cation. The threshold photoelectron measurement has allowed us to improve the determination of the ionization energy of 1-ethynylpyrene at 7.391 $\pm$ 0.005 eV. Concerning the main dissociation channels, the analysis of the breakdown graph has given 3.70 $\pm$ 0.60 eV as the activation energy for the loss of one H atom and 2.98 $\pm$ 1.80 eV for the loss of a second independent H atom. The corresponding entropies of activation are affected by large errors as observed in similar studies of other polycyclic aromatic hydrocarbon cations. Minor dissociation channels were also detected and identified as the loss of the C$_2$H group and the loss of a C$_2$H$_2$ unit and/or that of an H atom plus the C$_2$H group. The activation energies and the entropies of activation of these minor pathways could not be derived from the measurements. It is found that the cation of 1-ethynylpyrene behaves like the cation of pyrene and is consequently more photostable than the cation of 1-methylpyrene. We conclude that photodissociation is not the leading cause of the low abundance, if not the absence, of ethynyl-substituted polycyclic aromatic hydrocarbon species in the interstellar medium.

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G. Rouillé, M. Steglich, P. Hemberger, et. al.
Fri, 13 Sep 19
46/70

Comments: 13 pages, 9 figures, accepted for publication in The Astrophysical Journal

ExoMol molecular line lists XXXVI: $X\ {}^2Π- X\ {}^2Π$ and $A\ {}^2Σ^+ – X\ {}^2Π$ transitions of SH [EPA]

http://arxiv.org/abs/1909.02646


The GYT line list covering rotational, rovibrational and rovibronic transitions of the mercapto radical SH is presented. This work extends and replaces the SNaSH line list [Yurchenko et al., 2018, MNRAS, 478, 270] which covers the ground (electronic) $X$ $^{2}\Pi$ state only. This extension is prompted by the tentative identification of the ultra-violet features of SH as being of importance in the transmission spectrum of the ultra-hot Jupiter exoplanet WASP-121b [Evans et al., 2018, AJ., 156, 283]. This GYT line list model is generated by fitting empirical potential energy, spin-orbit and electronic angular momenta functions to experimentally measured wavelengths within the $X$ $^{2}\Pi$ and $A$ $^{2}\Sigma^{+}$ states and to the $A$ $^{2}\Sigma^{+}$ – $X$ $^{2}\Pi$ band system using ab initio curves as a starting reference point. The fits are compatible with the quoted uncertainty of the experimental data used of $\sim$ 0.03 – 0.3 cm$^{-1}$. The GYT line list covers wavelengths longer than 0.256 $\mu$m and includes 7686 rovibronic states and 572 145 transitions for $^{32}$SH. Line lists for the $^{33}$SH, $^{34}$SH, $^{36}$SH and $^{32}$SD isotopologues are generated including a consideration of non-Born-Oppenheimer effects for SD. The line lists are available from the CDS (this http URL) and ExoMol (www.exomol.com) data bases.

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M. Gorman, S. Yurchenko and J. Tennyson
Mon, 9 Sep 19
14/67

Comments: N/A

When did Life Likely Emerge on Earth in an RNA-First Process? [EPA]

http://arxiv.org/abs/1908.11327


The widespread presence of ribonucleic acid (RNA) catalysts and cofactors in Earth’s biosphere today suggests that RNA was the first biopolymer to support Darwinian evolution. However, most “path-hypotheses” to generate building blocks for RNA require reduced nitrogen-containing compounds not made in useful amounts in the CO2-N2-H2O atmospheres of the Hadean. We review models for Earth’s impact history that invoke a single ~10^23 kg impactor (Moneta) to account for measured amounts of platinum, gold, and other siderophilic (“iron-loving”) elements on the Earth and Moon. If it were the last sterilizing impactor, Moneta would have reduced the atmosphere but not its mantle, opening a “window of opportunity” for RNA synthesis, a period when RNA precursors rained from the atmosphere to land holding oxidized minerals that stabilize advanced RNA precursors and RNA. Surprisingly, this combination of physics, geology, and chemistry suggests a time when RNA formation was most probable, ~120 +/- 100 million years after Moneta’s impact, or ~4.36 +/- 0.1 billion years ago. Uncertainties in this time are driven by uncertainties in rates of productive atmosphere loss and amounts of sub-aerial land.

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S. Benner, E. Bell, E. Biondi, et. al.
Fri, 30 Aug 19
2/58

Comments: Paper accepted to ChemSystemsChem [this https URL] August 22, 2019

Graphene Oxide Nanoparticles in the Interstellar Medium [GA]

http://arxiv.org/abs/1908.07787


Dust particles play a major role in the formation, evolution and chemistry of interstellar clouds, stars and planetary systems. Commonly identified forms include amorphous and crystalline carbon-rich particles and silicates. Also present in many astrophysical environments are polycyclic aromatic hydrocarbons (PAHs), detected through their infrared emission, and which are essentially small flakes of graphene. Astronomical observations over the past four decades have revealed a widespread unassigned Extended Red Emission (ERE) feature which is attributed to luminescence of dust grains. Numerous potential carriers for ERE have been proposed but none has gained general acceptance. In this Letter it is shown that there is a strong similarity between laboratory optical emission spectra of graphene oxide and ERE, leading to this proposal that emission from graphene oxide nanoparticles is the origin of ERE and that these are a significant component of interstellar dust. The proposal is supported by infrared emission features detected by the Infrared Space Observatory (ISO) and the Spitzer Space Telescope.

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P. Sarre
Thu, 22 Aug 19
8/70

Comments: 5 pages, 3 figures

Rotational spectroscopy of methyl mercaptan CH$_3$$^{32}$SH at millimeter and submillimeter wavelengths [IMA]

http://arxiv.org/abs/1908.07790


We present a new global study of the millimeter (mm) wave, submillimeter (sub-mm) wave, and terahertz (THz) spectra of the lowest three torsional states of methyl mercaptan (CH$_3$SH). New measurements have been carried out between 50 and 510 GHz using the Kharkiv mm wave and the Cologne sub-mm wave spectrometers whereas THz spectra records were used from our previous study. The new data, involving torsion-rotation transitions with $J$ up to 61 and $K_a$ up to 18, were combined with previously published measurements and fit using the rho-axis-method torsion-rotation Hamiltonian. The final fit used 124 parameters to give an overall weighted root-mean-square deviation of 0.72 for the dataset consisting of 6965 microwave (MW) and 16345 far-infrared line frequencies sampling transitions within and between the ground, first, and second excited torsional states. This investigation presents a two-fold expansion in the $J$ quantum numbers and a significant improvement in the fit quality, especially for the MW part of the data, thus allowing us to provide more reliable predictions to support astronomical observations.

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O. Zakharenko, V. Ilyushin, F. Lewen, et. al.
Thu, 22 Aug 19
58/70

Comments: 12 pages; Astron. Astrophys., in press

The aromatic Universe [GA]

http://arxiv.org/abs/1908.05918


The rich molecular structures of polycyclic aromatic hydrocarbons — essentially planar flakes of fused benzene rings — and their fullerene cousins are revealed through their vibrational and electronic spectra.

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A. Candian, J. Zhen and A. Tielens
Mon, 19 Aug 19
6/46

Comments: The following article appeared in Physics Today, November 2018, page 38

Metallic liquid H3O in a thin-shell zone inside Uranus and Neptune [CL]

http://arxiv.org/abs/1908.05821


The Solar System harbors deep unresolved mysteries despite centuries-long study. A highly intriguing case concerns anomalous non-dipolar and non-axisymmetric magnetic fields of Uranus and Neptune that have long eluded explanation by the prevailing theory. A thin-shell dynamo conjecture captures observed phenomena but leaves unexplained fundamental material basis and underlying mechanism. Here, we report the discovery of trihydrogen oxide (H3O) in metallic liquid state stabilized at extreme pressure and temperature conditions inside these icy planets. Calculated stability pressure field compared to known pressure-radius relation for Uranus and Neptune places metallic liquid H3O in a thin-shell zone near planetary cores. These findings from accurate quantum mechanical calculations rationalize the empirically conjectured thin-shell dynamo model and establish key physical benchmarks that are essential to elucidating the enigmatic magnetic-field anomaly of Uranus and Neptune, resolving a major mystery in planetary science.

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P. Huang, H. Liu, J. Lv, et. al.
Mon, 19 Aug 19
44/46

Comments: N/A

The Photolysis of Aromatic Hydrocarbons Adsorbed on the Surfaces of Cosmic Dust Grains [GA]

http://arxiv.org/abs/1908.04356


The work is devoted to the adaptation of the results of laboratory studies of the laser-induced dissociation of molecules of benzene adsorbed on a quartz substrate to the conditions of the interstellar medium. Adsorption was performed under conditions of low temperature and deep vacuum. The difference between the photolysis of adsorbed molecules and molecules in the gas phase is identified. Significance of process of photolytic desorption in the interstellar conditions is analyzed, in particular, in the conditions of photodissociation regions. It is shown that the efficiency and dissociation channels of photolysis of adsorbed and gas phase benzene differ substantially. It is concluded that the photolysis of aromatic hydrocarbons adsorbed on the interstellar dust grains contributes a negligible fraction to the abundance of small hydrocarbons in the interstellar medium.

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M. Murga, V. Varakin, A. Stolyarov, et. al.
Wed, 14 Aug 19
15/60

Comments: The original paper is published in Astronomy Reports. The paper includes 17 pages, 3 figures

The water line emission and ortho-to-para ratio in the Orion Bar photon-dominated region [GA]

http://arxiv.org/abs/1908.00268


A very low ortho-to-para ratio (OPR) of 0.1-0.5 was previously reported in the Orion Bar photon-dominated region (PDR), based on observations of two optically thin $\mathrm{H_2^{18}O}$ lines which were analyzed by using a single-slab large velocity gradient model. The corresponding spin temperature does not coincide with the kinetic temperature of the molecular gas in this UV-illuminated region. This was interpreted as an indication of water molecules being formed on cold icy grains which were subsequently released by UV photodesorption. A more complete set of water observations in the Orion Bar, including seven $\mathrm{H_2^{16}O}$ lines and one $\mathrm{H_2^{18}O}$ line, carried out using Herschel/HIFI instrument, was reanalyzed using the Meudon PDR code to derive gas-phase water abundance and the OPR, taking into account the steep density and temperature gradients present in the region. The model line intensities are in good agreement with the observations assuming that water molecules formed with an OPR corresponding to thermal equilibrium conditions at the local kinetic temperature of the gas and when solely considering gas-phase chemistry and water gas-grain exchanges through adsorption and desorption. Gas-phase water is predicted to arise from a region deep into the cloud, corresponding to a visual extinction of $A_{\mathrm{V}} \sim 9$, with a $\mathrm{H_2^{16}O}$ fractional abundance of $\sim 2\times 10^{-7}$ and column density of $(1.4 \pm 0.8) \times 10^{15}$ cm$^{-2}$ for a total cloud depth of $A_{\mathrm{V}}=15$. A line-of-sight average ortho-to-para ratio of $2.8 \pm 0.1$ is derived. The observational data are consistent with a nuclear spin isomer repartition corresponding to the thermal equilibrium at a temperature of $35 \pm 2$ K, much higher than the spin temperature previously reported for this region and close to the gas kinetic temperature in the water-emitting gas.

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T. Putaud, X. Michaut, F. Petit, et. al.
Fri, 2 Aug 19
20/61

Comments: N/A

The Fundamental Vibrational Frequencies and Spectroscopic Constants of the Dicyanoamine Anion, NCNCN$^-$ (C$_2$N$_3^-$): Quantum Chemical Analysis for Astrophysical and Planetary Environments [EPA]

http://arxiv.org/abs/1907.10366


Detecting anions in space has relied on a strong collaboration between theoretical and laboratory analyses to measure rotational spectra and spectroscopic constants to high accuracy. The advent of improved quantum chemical tools operating at higher accuracy and reduced computational cost is a crucial solution for the fundamental characterization of astrophysically-relevant anions and their detection in the interstellar medium and planetary atmospheres. In this context, we have turned towards the quantum chemical analysis of the penta-atomic dicyanoamine anion NCNCN$^-$ (C$_2$N$_3^-$), a structurally bent and polar compound. We have performed high-level coupled cluster theory quartic force field (QFF) computations of C$_2$N$_3^-$ satisfying both computational cost and accuracy conditions. We provide for the first time accurate spectroscopic constants and vibrational frequencies for this ion. In addition to exhibiting various Fermi resonances, C$_2$N$_3^-$ displays a bright $\nu$2 (2130.9 cm$^{-1}$) and a less intense $\nu$1 (2190.7 cm$^{-1}$) fundamental vibrational frequency, making for strong markers for future infrared observations < 5$\mu$m. We have also determined near-IR overtone and combination bands of the bright fundamentals for which the 2$\nu$2 at 4312.1 cm$^{-1}$ (2.319 $\mu$m) is the best candidate. C$_2$N$_3^-$ could potentially exist and be detected in nitrogen-rich environments of the ISM such as IRC +10216 and other carbon-rich circumstellar envelopes, or in the atmosphere of Saturn’s moon Titan, where advanced N-based reactions may lead to its formation.

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D. Dubois, E. Sciamma-O’Brien and R. Fortenberry
Thu, 25 Jul 19
66/72

Comments: 20 pages, 1 figure, 3 tables, Accepted for publication in The Astrophysical Journal

Anharmonicity in the mid-infrared spectra of polycyclic aromatic hydrocarbons: Molecular beam spectroscopy and calculations [GA]

http://arxiv.org/abs/1907.09351


Aims. In this work we determine the effects of anharmonicity on the mid-infrared spectra of the linear polycyclic aromatic hydrocarbons (PAHs) naphthalene, anthracene, tetracene and pentacene recorded using the free electron laser FELIX. Methods. Comparison of experimental spectra obtained under supersonic jet conditions with theoretically predicted spectra was used to show if anharmonicity explicitly needs to be taken into account. Results. Anharmonic spectra obtained using second-order vibrational perturbation theory agree on average within 0.5% of the experimental frequencies. Importantly, they confirm the presence of combination bands with appreciable intensity in the 5-6 $\mu$m region. These combination bands contain a significant fraction of the IR absorption, which scales linearly with the size of the PAH. Detection and assignment of the combination bands are a preliminary indication of the accuracy of far-IR modes in our anharmonic theoretical spectra. Detailed analysis of the periphery-sensitive CH out-of-plane band of naphthalene reveals that there is still room for improvement of the VPT2 approach. In addition, the implications of our findings for the analysis of the aromatic infrared bands are discussed.

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A. Lemmens, D. Rap, J. Thunnissen, et. al.
Tue, 23 Jul 19
38/72

Comments: 10 pages, 3 figures and Appendix. Accepted in Astronomy and Astrophysics

Laboratory rotational spectroscopy of isotopic acetone, CH$_3^{13}$C(O)CH$_3$ and $^{13}$CH$_3$C(O)CH$_3$, and astronomical search in Sagittarius B2(N2) [GA]

http://arxiv.org/abs/1907.08073


We want to study the rotational spectra of CH$_3^{13}$C(O)CH$_3$ and $^{13}$CH$_3$C(O)CH$_3$ and search for them in Sagittarius B2(N2). We investigated the laboratory rotational spectrum of isotopically enriched CH$_3^{13}$C(O)CH$_3$ between 40 GHz and 910 GHz and of acetone between 36 GHz and 910 GHz in order to study $^{13}$CH$_3$C(O)CH$_3$ in natural isotopic composition. In addition, we searched for emission lines produced by these species in a molecular line survey of Sagittarius B2(N) carried out with ALMA. Discrepancies between predictions of the main isotopic species and the ALMA spectrum prompted us to revisit the rotational spectrum of this isotopolog. We assigned 9711 new transitions of CH$_3^{13}$C(O)CH$_3$ and 63 new transitions of $^{13}$CH$_3$C(O)CH$_3$ in the laboratory spectra. More than 1000 additional lines were assigned for the main isotopic species. We modeled the ground state data of all three isotopologs satisfactorily with the ERHAM program. We find that models of the torsionally excited states $v _{12} = 1$ and $v _{17} = 1$ of CH$_3$C(O)CH$_3$ improve only marginally. No transition of CH$_3^{13}$C(O)CH$_3$ is clearly detected toward the hot molecular core Sgr B2(N2). However, we report a tentative detection of $^{13}$CH$_3$C(O)CH$_3$ with a $^{12}$C/$^{13}$C isotopic ratio of 27 that is consistent with the ratio previously measured for alcohols in this source. Several dozens of transitions of both torsional states of the main isotopolog are detected as well. Our predictions of CH$_3^{13}$C(O)CH$_3$ and CH$_3$C(O)CH$_3$ are reliable into the terahertz region. The spectrum of $^{13}$CH$_3$C(O)CH$_3$ should be revisited in the laboratory with an enriched sample. Transitions pertaining to the torsionally excited states $v _{12} = 1$ and $v _{17} = 1$ of CH$_3$C(O)CH$_3$ could be identified unambiguously in Sagittarius B2(N2).

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M. Ordu, O. Zingsheim, A. Belloche, et. al.
Fri, 19 Jul 19
26/78

Comments: A&A in press; Abstract abbreviated; 37 pages: 12 pages + 25 pages Appendix

Chemistry on Rotating Grain Surface: Ro-Thermal Desorption of Molecules from Ice Mantles [GA]

http://arxiv.org/abs/1906.11386


It is widely believed that water and complex organic molecules (COMs) first form in the ice mantle of dust grains and are subsequently returned into the gas due to grain heating by intense radiation of protostars. Previous research on the desorption of molecules from the ice mantle assumed that grains are at rest, which is contrary to the fact that grains are suprathermally rotating as a result of their interaction with an anisotropic radiation or gas flow. Toward an era of precision astrochemistry, the effect of grain rotation on surface chemistry must be quantified. In this paper, we study the effect of suprathermal rotation of dust grains spun-up by radiative torques on the desorption of molecules from icy grain mantles around protostars. We show that centrifugal potential energy due to grain rotation reduces the potential barrier of molecules and significantly enhances their desorption rate. We term this mechanism {\it rotational-thermal} or {\it ro-thermal} desorption. We apply the ro-thermal mechanism for studying the desorption of molecules from icy grains which are simultaneously heated to high temperatures and spun-up to suprathermal rotation by an intense radiation of protostars. We find that ro-thermal desorption is much more efficient than thermal desorption for molecules with high binding energy such as water and COMs. Our results have important implications for understanding the origin of COMs detected in star-forming regions and call for attention to the effect of suprathermal rotation of icy grains to use molecules as a tracer of physical conditions of star-forming regions.

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T. Hoang and N. Tung
Fri, 28 Jun 19
27/65

Comments: 9 figures, 16 pages, to be submitted

Collisional excitation of NH(3Σ-) by Ar: A new ab initio 3D potential energy surface and scattering calculations [CL]

http://arxiv.org/abs/1906.11474


Collisional excitation of light hydrides is important to fully understand the complex chemical and physical processes of atmospheric and astrophysical environments. Here, we focus on the NH(X3{\Sigma}-)-Ar van der Waals system. First, we have calculated a new three-dimensional Potential Energy Surface (PES), which explicitly includes the NH bond vibration. We have carried out the ab initio calculations of the PES employing the open-shell single- and double-excitation couple cluster method with noniterative perturbational treatment of the triple excitations. To achieve a better accuracy, we have first obtained the energies using the augmented correlation-consistent aug-cc-pVXZ (X = T, Q, 5) basis sets and then we have extrapolated the final values to the complete basis set limit. We have also studied the collisional excitation of NH(X3{\Sigma}-)-Ar at the close-coupling level, employing our new PES. We calculated collisional excitation cross sections of the fine-structure levels of NH by Ar for energies up to 3000 cm-1 . After thermal average of the cross sections, we have then obtained the rate coefficients for temperatures up to 350 K. The propensity rules between the fine-structure levels are in good agreement with those of similar collisional systems, even though they are not as strong and pronounced as for lighter systems, such as NH-He. The final theoretical values are also compared with the few available experimental data.

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D. Prudenzano, F. Lique, R. Ramachandran, et. al.
Fri, 28 Jun 19
36/65

Comments: N/A

Unconventional phase III of high-pressure solid hydrogen [CL]

http://arxiv.org/abs/1906.10854


We reassess the phase diagram of high-pressure solid hydrogen using mean-filed and many-body wave function based approaches to determine the nature of phase III of solid hydrogen. To discover the best candidates for the phase III, Density Functional Theory with meta-generalized-gradient approximation (meta-GGA) non-empirical strongly constrained and appropriately normed (SCAN) exchange-correlation (XC) is employed. We study eleven molecular structures with different symmetry, which are the most competitive phases, within the pressure range of 100 to 500 GPa. The SCAN phase diagram predicts that the $C2/c-24$ and $P6_122-36$ structures are the best candidates for the phase III with energy difference of less than 1 meV/atom. To verify the stability of the competitive insulator structures of $C2/c-24$ and $P6_122-36$, we apply the diffusion quantum Monte Carlo (DMC) to optimise the percentage of the exact exchange ($\alpha$) in the trial many-body wave function. We found that the optimised $\alpha$ equals to $40 \%$, and the corresponding XC functional is named PBE${1x}$. The energy gain with respect to the conventional hybrid functional (PBE$_0$) with $\alpha = 25\%$ varies with density and structure. The PBE${1x}$-DMC enthalpy-pressure phase diagram predicts that the $P6_122-36$ structure is stable up to 210 GPa where it transforms to the $C2/c-24$. We predict that the phase III of high-pressure solid hydrogen is polymorphic.

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S. Azadi and T. Kuehne
Thu, 27 Jun 19
62/62

Comments: N/A

Discovery of the first Ca-bearing molecule in space: CaNC [SSA]

http://arxiv.org/abs/1906.09352


We report on the detection of calcium isocyanide, CaNC, in the carbon-rich evolved star IRC+10216. We derived a column density for this species of (2.0$\pm$0.5)$\times$10$^{11}$ cm$^{-2}$. Based on the observed line profiles and the modelling of its emission through the envelope, the molecule has to be produced in the intermediate and outer layers of the circumstellar envelope where other metal-isocyanides have previously been found in this source. The abundance ratio of CaNC relative to MgNC and FeCN is $\simeq$1/60 and $\simeq$1, respectively. We searched for the species CaF, CaCl, CaC, CaCCH, and CaCH$_3$ for which accurate frequency predictions are available. Only upper limits have been obtained for these molecules.

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J. Cernicharo, L. Velilla-Prieto, M. Agúndez, et. al.
Tue, 25 Jun 19
24/68

Comments: 5 pages, 2 figures, accepted for publication in A&A

Amino Acid Chiral Selection Via Weak Interactions in Stellar Environments: Implications for the Origin of Life [EPA]

http://arxiv.org/abs/1906.08623


Magnetochiral phenomena may be responsible for the selection of chiral states of biomolecules in meteoric environments. For example, the Supernova Amino Acid Processing (SNAAP) Model was proposed previously as a possible mode of magnetochiral selection of amino acids by way of the weak interaction in strong magnetic fields. In earlier work, this model was shown to produce an enantiomeric excess (ee) as high as 0.014% for alanine. In this paper we present the results of molecular quantum chemistry calculations from which $ee$s are determined for the alpha-amino acids plus isovaline and norvaline, which were found to have positive ees in meteorites. Calculations are performed for both isolated and aqueous states. In some cases, the aqueous state was found to produce larger $ee$s reaching values as high as a few percent under plausible conditions.

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M. Famiano, R. Boyd, T. Kajino, et. al.
Fri, 21 Jun 19
30/56

Comments: N/A

Mutual neutralization in Li$^+$-D$^-$ collisions: a combined experimental and theoretical study [CL]

http://arxiv.org/abs/1906.06715


We present a combined experimental and theoretical study of the mutual neutralization process in collisions of lithium ions (Li+) with deuterium anions (D-) at collision energies below 1 eV. We employ a merged-beam apparatus to determine total and state-to-state mutual neutralization cross sections. We perform nuclear dynamics calculations using the multi-channel Landau-Zener model based on accurate ab initio molecular data. We obtain an excellent agreement between the experimental and theoretical results over the energy range covered in this work. We show that the basis sets used in the ab initio calculations have a limited influence on the total cross section, but strongly impacts the results obtained for the partial cross sections or the reaction branching ratios. This demonstrates the important role of high-precision measurements to validate the theoretical approaches used to study gas-phase reactive processes. Finally, we compute mutual neutralization rate coefficients for Li+ + H- and Li+ + D-, and discuss their significance for astrochemistry models.

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T. Launoy, J. Loreau, A. Dochain, et. al.
Tue, 18 Jun 19
9/73

Comments: N/A

Rotational spectroscopy of isotopic species of methyl mercaptan at millimeter and submillimeter wavelengths: CH$_3$$^{34}$SH [SSA]

http://arxiv.org/abs/1906.00897


Methyl mercaptan (CH$_3$SH) is an important sulfur-bearing species in the interstellar medium, terrestrial environment, and potentially in planetary atmospheres. The aim of the present study is to provide accurate spectroscopic parameters for the most abundant minor isotopolog CH$_3$$^{34}$SH to support radio astronomical observations at millimeter and submillimeter wavelengths. The rotational spectrum of CH$_3$$^{34}$SH, which is complicated by the large-amplitude internal rotation of the CH$_3$ group versus the $^{34}$SH frame, was investigated in the 49$-$510 GHz and 1.1$-$1.5 THz frequency ranges in natural isotopic abundance. The analysis of the spectrum was performed up to the second excited torsional state, and the obtained data were modeled with the RAM36 program. A fit within experimental accuracy was obtained with a RAM Hamiltonian model that uses 72 parameters. Predictions based on this fit are used to search for CH$_3$$^{34}$SH with the Atacama Large Millimeter/submillimeter Array (ALMA) toward the hot molecular core Sgr B2(N2), but blends with emission lines of other species prevent its firm identification in this source.

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O. Zakharenko, F. Lewen, V. Ilyushin, et. al.
Tue, 4 Jun 19
52/71

Comments: 8 pages, Astron. Astrophys., in press

No compelling evidence for clathrate hydrate formation under interstellar medium conditions over laboratory timescales [EPA]

http://arxiv.org/abs/1905.11209


A recent article reported experimental observations of methane and CO2 clathrate formation at conditions similar to the interstellar medium (ISM), namely 10-30 K and 10-10 mbar. The authors conducted time-dependent reflection-absorption infrared spectroscopy (RAIRS) of vapor-deposited H2O:CH4 and H2O:CO2 mixtures and interpreted new blue and red -shifted peaks from those of trapped CH4 and CO2 in amorphous ice, respectively, as indicative of clathrate formation. In this Letter to the Editor, we point out potential pitfalls and caution against the implications drawn for the ISM.

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M. Choukroun, T. Vu and E. Fayolle
Tue, 28 May 19
46/82

Comments: Letter to the Editor, Proceedings of the National Academy of Sciences

Ab initio spectroscopic characterization of the radical CH$_3$OCH$_2$ at low temperatures [CL]

http://arxiv.org/abs/1905.09506


Spectroscopic and structural properties of methoxymethyl radical (CH$_3$OCH$_2$, RDME) are determined using explicitly correlated ab initio methods. This radical of astrophysical and atmospheric relevance has not been fully characterized at low temperatures, which has delayed the astrophysical searches. We provide rovibrational parameters, excitations to the low energy electronic states, torsional and inversion barriers and low vibrational energy levels. In the electronic ground state (X$^2$A), which appears “clean” from non-adiabatic effects, the minimum energy structure is an asymmetric geometry which rotational constants and dipole moment have been determined to be A$_0$=46718.6745 MHz, B$_0$=10748.4182 MHz, and C$_0$=9272.5105 MHz, and 1.432 D ($\mu_A$=0.6952 D, $\mu_B$=1.215 D, $\mu_C$=0.3016 D), respectively. A variational procedure has been applied to determine torsion-inversion energy levels. Each level splits into 3 subcomponents (A$_1$/A$_2$ and E) corresponding to the three methyl torsion minima. Although the potential energy surface presents 12 minima, at low temperatures, the infrared band shapes correspond to a surface with only three minima because the top of the inversion V$^{\alpha}$ barrier at ${\alpha}=0^{\circ}$ (109 cm$^{-1}$) stands below the zero point vibrational energy and the CH$_2$ torsional barrier is relatively high ($\sim$2000 cm$^{-1}$). The methyl torsion barrier was computed to be $\sim$500 cm$^{-1}$ and produces a splitting of 0.01 cm$^{-1}$ of the ground vibrational state.

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O. Yazidi, M. Senent, V. Gámez, et. al.
Fri, 24 May 19
54/60

Comments: N/A

Vacuum ultraviolet photodesorption and photofragmentation of formaldehyde-containing ices [GA]

http://arxiv.org/abs/1905.08223


Non-thermal desorption from icy grains containing H$_2$CO has been invoked to explain the observed H$_2$CO gas phase abundances in ProtoPlanetary Disks (PPDs) and Photon Dominated Regions (PDRs). Photodesorption is thought to play a key role, however no absolute measurement of the photodesorption from H$_2$CO ices were performed up to now, so that a default value is used in the current astrophysical models. As photodesorption yields differ from one molecule to the other, it is crucial to experimentally investigate photodesorption from H$_2$CO ices.
We measured absolute wavelength-resolved photodesorption yields from pure H$_2$CO ices, H$_2$CO on top of a CO ice (H$_2$CO/CO), and H$_2$CO mixed with CO ice (H$_2$CO:CO) irradiated in the Vacuum UltraViolet (VUV) range (7-13.6~eV). Photodesorption from a pure H$_2$CO ice releases H$_2$CO in the gas phase, but also fragments, such as CO and H$_2$. Energy-resolved photodesorption spectra, coupled with InfraRed (IR) and Temperature Programmed Desorption (TPD) diagnostics, showed the important role played by photodissociation and allowed to discuss photodesorption mechanisms. For the release of H$_2$CO in the gas phase, they include Desorption Induced by Electronic Transitions (DIET), indirect DIET through CO-induced desorption of H$_2$CO and photochemical desorption.
We found that H$_2$CO photodesorbs with an average efficiency of $\sim 4-10 \times 10^{-4}$ molecule/photon, in various astrophysical environments. H$_2$CO and CO photodesorption yields and photodesorption mechanisms, involving photofragmentation of H$_2$CO, can be implemented in astrochemical codes. The effects of photodesorption on gas/solid abundances of H$_2$CO and all linked species from CO to Complex Organic Molecules (COMs), and on the H$_2$CO snowline location, are now on the verge of being unravelled.

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G. Féraud, M. Bertin, C. Romanzin, et. al.
Tue, 21 May 19
61/71

Comments: ACS Earth and Space Chemistry; Complex Organic Molecules (COMs) in Star-Forming Regions special issue

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

http://arxiv.org/abs/1905.07801


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

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D. Qasim, G. Fedoseev, K. Chuang, et. al.
Tue, 21 May 19
69/71

Comments: Accepted for publication in Astronomy and Astrophysics

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

http://arxiv.org/abs/1905.06767


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

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D. Qasim, T. Lamberts, K. Chuang, et. al.
Fri, 17 May 19
19/59

Comments: Accepted for publication in Astronomy and Astrophysics

A Variationally Computed IR Line List for the Methyl Radical CH$_3$ [CL]

http://arxiv.org/abs/1905.05504


We present the first variational calculation of a hot temperature ab initio line list for the CH$_3$ radical. It is based on a high level ab initio potential energy surface and dipole moment surface of CH$_3$ in the ground electronic state. The ro-vibrational energy levels and Einstein $A$ coefficients were calculated using the general-molecule variational approach implemented in the computer program TROVE. Vibrational energies and vibrational intensities are found to be in very good agreement with the available experimental data. The line list comprises 9,127,123 ro-vibrational states ($J\le 40$) and 2,058,655,166 transitions covering the wavenumber range up to 10000 cm$^{-1}$ and should be suitable for temperatures up to $T= 1500$ K.

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A. Adam, A. Yachmenev, S. Yurchenko, et. al.
Wed, 15 May 19
32/57

Comments: N/A

Theoretical rotation-vibration spectroscopy of {\it cis}- and {\it trans}-diphosphene (P$_2$H$_2$) and the deuterated species P$_2$HD [CL]

http://arxiv.org/abs/1905.04990


Growing astronomical interest in phosphorous (P) chemistry is stimulating the search for new interstellar P-bearing molecules; a task requiring detailed knowledge of the microwave and infrared molecular spectrum. In this work, we present comprehensive rotation-vibration line lists of the \cis- and \trans-isomers of diphosphene (P$_2$H$_2$). The line lists have been generated using robust, first-principles methodologies based on newly computed, high-level \ai\ potential energy and dipole moment surfaces. Transitions are considered between states with energies up to $8000$~cm$^{-1}$ and total angular momentum $J\leq25$. These are the first-ever line lists to be reported for P$_2$H$_2$ and they should significantly facilitate future spectroscopic characterization of this system. The deuterated species \trans-P$_2$HD and the effect of its dynamic dipole moment on the rovibrational spectrum is also discussed.

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A. Owens and S. Yurchenko
Tue, 14 May 19
11/91

Comments: N/A

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

http://arxiv.org/abs/1905.05063


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

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D. Qasim, G. Fedoseev, T. Lamberts, et. al.
Tue, 14 May 19
46/91

Comments: Published in ACS Earth and Space Chemistry, Complex Organic Molecules (COMs) in Star-Forming Regions special issue

ExoMol Molecular linelists – XXXIII. The spectrum of Titanium Oxide [SSA]

http://arxiv.org/abs/1905.04587


Accurate line lists are crucial for correctly modelling a variety of astrophysical phenomena, including stellar photospheres and the atmospheres of extra-solar planets. This paper presents a new line database Toto for the main isotopologues of titanium oxide (TiO): $^{46}$Ti$^{16}$O, $^{47}$Ti$^{16}$O, $^{48}$Ti$^{16}$O, $^{49}$Ti$^{16}$O and $^{50}$Ti$^{16}$O. The TiO line list molecule containing transitions with wave-numbers up to 30,000 cm$^{-1}$ ie long-wards of 0.33 $\mu$m. The Toto line list includes all dipole-allowed transitions between 13 low-lying electronic states (X $^3\Delta$, a $^1\Delta$, d $^1\Sigma^+$, E $^3\Pi$, A $^3\Phi$ B $^3\Pi$, C $^3\Delta$, b $^1\Pi$, c $^1\Phi$, f $^1\Delta$, e $^1\Sigma^+$). Ab initio potential energy curves (PECs) are computed at the icMRCI level and combined with spin-orbit and other coupling curves. These PECs and couplings are iteratively refined to match known empirical energy levels. Accurate line intensities are generated using ab initio dipole moment curves. The Toto line lists are appropriate for temperatures below 5000 K and contain 30 million transitions for TiO; it is made available in electronic form via the CDS data centre and via www.exomol.com. Tests of the line lists show greatly improved agreement with observed spectra for objects such as M-dwarfs GJ876 and GL581.

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L. McKemmish, T. Masseron, H. Hoeijmakers, et. al.
Tue, 14 May 19
89/91

Comments: N/A