Astrophysical Media Research Articles

Vacuum Ultraviolet Single Photon Ionization and Decomposition of 2-Aminopropionitrile in Astrophysical Objects

The molecule 2-aminopropionitrile (2-APN; H3CCH(NH2)CN) is a chiral precursor of the amino acid alanine and could play an important role in the emergence of the homochirality of life. To date, 2-APN has not yet been detected in the interstellar medium. To address the question of its absence, possibly through destruction by vacuum ultraviolet radiation in astrophysical media, we studied its photoionization and dissociative photoionization in the 9–14 eV (89–137 nm) energy range using photoelectron–photoion coincidence spectroscopy with velocity map imaging. Density functional theory calculations were performed at the PBE0/aug-cc-pVTZ level to determine structures for the various cationic fragments identified experimentally. Their appearance energies were calculated. The adiabatic ionization energy (AIE) of 2-APN is AIE = (9.85±0.01) eV and the appearance energy (AE) of the major fragment ion N≡CC(H)NH2 + is AE = (10.57±0.01) eV. Both ions, 2-APN+ and N≡CC(H)NH2 +, make up more than 90% of the formed ions. N≡CC(H)NH2 +, an isomer of the protonated HCN dimer, is also formed with high yield in the dissociative photoionization of aminoacetonitrile (NH2CH2CN), another α-aminonitrile observed in Sgr B2(N). Photoion yield spectra have been calibrated to absolute ionization cross sections. From these, we derive photoionization rates in several typical radiation fields relevant to different astrophysical objects. The rates show that, under almost all explored radiation fields, dissociative ionization is the dominant pathway for photoionization, leading to the loss of a methyl group (CH3) to form the planar thermodynamically stable amino cyano methylidynium ion N≡CC(H)NH2 +. The observed absence of 2-APN in Sgr B2 could thus be due to dominant dissociative photoionization.

Rotational excitation and de-excitation of interstellar chloronium cation in collisions with helium atoms

Abstract Chloronium, H2Cl+, is detected in astrophysical media. It is key chemical intermediate for understanding of the physical chemistry of chlorine species there. At present, we compute the collision rates for the rotational excitation and de-excitation of ortho- and para-H2Cl+ colliding with He for T ≤ 150 K, relevant for the interstellar medium (ISM) conditions. Prior to that, we generated the 3D interaction potential of the weakly bound H2Cl+-He complex along the Jacobi coordinates. For electronic structure computations, we used a post-Hartree-Fock explicitly correlated method at the CCSD(T)-F12/aug-cc-pVTZ level. The analytical expansion of this potential was incorporated into close coupling computations of the cross-sections for the rotational excitation and de-excitation of ortho- and para-H2Cl+ colliding with He and for collision kinetic energies Ek ≤ 1000 cm−1. The rates were obtained after averaging these cross-sections over a Maxwell–Boltzmann distribution of kinetic energies. Our data show that the ∆j=∆ka=∆kc=−1 de-excitation transitions exhibit the largest values, in particular those used to identify this cation in the surveys. Besides, our results should help for determining more accurate abundances of H2Cl+ in the ISM and thus better modelling the chlorine chemistry there.

Fine-structure excitation of CCS by He: Potential energy surface and scattering calculations.

The fine structure excitation of the interstellar CCS radical induced by collisions with He is investigated. The first potential energy surface (PES) for the CCS-He van der Waals complex is presented. It was obtained from a highly correlated spin unrestricted coupled cluster approach with single double and perturbative triple excitations. The PES presents two shallow minima of 31.85 and 37.12 cm-1 for the linear (He facing S) and the nearly T-shaped geometries, respectively. The dissociation energy of the complex was calculated and found to be D0 = 14.183 cm-1. Inelastic scattering calculations were performed using the close-coupling approach. Cross-sections for transitions between the 61 first fine structure levels of CCS were obtained for energy up to 600 cm-1 and rate coefficients for the 5-50K temperature range were derived. This set of collisional data can be used to model CCS emission spectra in dark molecular interstellar clouds and circumstellar envelopes and enable an accurate determination of CCS abundance in these astrophysical media.

The spectral features and detectability of small, cyclic silicon carbide clusters

Rovibrational spectral data for several tetra-atomic silicon carbide clusters (TASCCs) are computed in this work using a CCSD(T)-F12b/cc-pCVTZ-F12 quartic force field. Accurate theoretical spectroscopic data may facilitate the observation of TASCCs in the interstellar medium which may lead to a more complete understanding of how the smallest silicon carbide (SiC) solids are formed. Such processes are essential for understanding SiC dust grain formation. Due to SiC dust prevalence in the interstellar medium, this may also shed light on subsequent planetary formation. Rhomboidal Si2C2 is shown here to have a notably intense (247 km mol−1) anharmonic vibrational frequency at 988.1 cm−1 (10.1 μm) for ν2, falling into one of the spectral emission features typically associated with unknown infrared bands of various astronomical regions. Notable intensities are also present for several of the computed anharmonic vibrational frequencies including the cyclic forms of C4, SiC3, Si3C, and Si4. These features in the 6–10 μm range are natural targets for infrared observation with the James Webb Space Telescope (JWST)’s MIRI instrument. Additionally, t-Si2C2, d-Si3C, and r-SiC3 each possess dipole moments of greater than 2.0 D making them interesting targets for radioastronomical searches especially since d-SiC3 is already known in astrophysical media.

A statistical investigation of the rate constants for the H+ + HD reaction at temperatures of astrophysical interest.

The H+ + HD(v, j) reaction has been investigated in detail by means of a statistical quantum method. State-to-state cross sections and rate constants for transitions between reactants and rovibrational states HD(v', j') of the product arrangement with energies below 0.9eV collision energy [that is, HD(v = 0, j = 0-11) and HD(v = 1, j = 0-6)] have been calculated. For the other product channel, D+ + H2(v', j'), rovibrational states up to (v' = 0, j' = 9) have been considered for the calculation of the corresponding thermal rate. Present predictions are compared with previously reported theoretical and experimental rates. Finally, cooling functions for HD due to proton and atomic hydrogen collisions are computed in the low-density regime. We find that the much larger HD-H+ cooling function, as compared with that of HD-H, does not compensate for the low H+/H abundance ratio in astrophysical media so that HD cooling is dominated by HD-H (or HD-H2) collisions.

Quantification of molecular aromaticity as a predictive factor of astrophysical significance

Context. This study reports the index of aromaticity calculated by numerical integration of the magnetically-induced current density for cyclic hydrocarbon molecules both known to exist in astrophysical media as well as those proposed to exist. Aims. This study promotes the ring current strength (RCS) value for quantifying aromaticity as a means of predicting astrophysical detectability. Methods. Density functional theory (DFT) calculations at the B3LYP/aug-cc-pVTZ level provide optimized structures and the wave-functions needed to provide the RCS values for the molecules analyzed. Results. The known interstellar molecules examined c-C3H2, c-(O)C3H2, c-C3HC2H, o-benzyne, benzonitrile, 1-cyano and 2-cyanonaphthalene all have RCS values of 9.9 nA T−1 (nanoampere per Tesla) or above. The known antiaromatic species have RCS values of less than 0.0 nA T−1 as expected. Several proposed interstellar molecules likely will not persist if they form due to low RCS values including c-(C)C3H2. Other species such as p-benzyne and c-HCNN+ have high RCS values of 19.9 nAT−1 and 14.4nAT−1, respectively. Conclusions. Cyclic hydrocarbons previously observed in astrophysical media have high RCS values. Those with low or negative RCS values have yet to be observed implying that such a metric can indicate astrophysical significance.

Collision excitation of c-C3H-(X1A1) by He.

Accurate modeling of anionic abundances in the interstellar and circumstellar media requires calculations of collisional data with the most abundant species that are usually He atoms and H2 molecules. In this paper, we focus on smaller cyclic molecular anion, c-C3H-, an astrophysical candidate, following the detection of larger CnH- carbon chains. From a new three-dimensional potential energy surface, the rotational (de-)excitation of the c-C3H-(X1A1) anion by collision with He is investigated. The surface is obtained in the supermolecular approach at the CCSD(T)-F12/aug-cc-pVTZ level of theory. Fully quantum close-coupling calculations of inelastic integral cross sections are performed on a grid of collisional energies large enough to ensure the convergence of the state-to-state rate coefficients for the 34 first rotational levels up to jKa,Kc = 77,0 of c-C3H- and temperatures ranging from 5 to 100K. For this collisional system, rate coefficients exhibit a strong dominance in favor of 21,2 → l1,1 downward transition. This transition was previously used for the detection of the cyclic parent c-C3H. The c-C3H--He rate coefficients (∼10-11cm3s-1) are of the same order of magnitude as those of the detected anions CnH- (as C2H-, C4H-, and C6H-) in collision with He and one order of magnitude smaller than those with H2. The critical densities of H2 were also estimated, and a discussion on the validity of the local thermodynamic equilibrium conditions is carried out. This work represents the contribution to understanding and modeling abundances and chemistry of hydrocarbon radicals, CnH, in astrophysical media.

Dark matter scattering in astrophysical media: collective effects

It is well-known that stars have the potential to be excellent dark matter detectors. Infalling dark matter that scatters within stars could lead to a range of observational signatures, including stellar heating, black hole formation, and modified heat transport. To make robust predictions for such phenomena, it is necessary to calculate the scattering rate for dark matter inside the star. As we show in this paper, for small enough momentum transfers, this requires taking into account collective effects within the dense stellar medium. These effects have been neglected in many previous treatments; we demonstrate how to incorporate them systematically, and show that they can parametrically enhance or suppress dark matter scattering rates depending on how dark matter couples to the Standard Model. We show that, as a result, collective effects can significantly modify the potential discovery or exclusion reach for observations of compact objects such as white dwarfs and neutron stars. While the effects are more pronounced for dark matter coupling through a light mediator, we show that even for dark matter coupling via a heavy mediator, scattering rates can differ by orders of magnitude from their naive values for dark matter masses ≲ 100 MeV. We also illustrate how collective effects can be important for dark matter scattering in more dilute media, such as the Solar core. Our results demonstrate the need to systematically incorporate collective effects in a wide range of astroparticle contexts; to facilitate this, we provide expressions for in-medium self-energies for a variety of different media, which are applicable to many other processes of interest (such as particle production).

General formulation of interactions and energy loss of particles in plasmas: Quantum-wave-packet model versus a semiclassical approach

In this work we present a general quantum-mechanical and statistical formulation of the process of interactions of external test particles with plasmas, considering the calculation of the energy-loss coefficients, including energy losses, mean-free paths, and straggling, and describing in detail the differences between protons, positrons, and electrons. Two relevant aspects contained in this formulation are studied: the competing action of loss and gain processes in the interaction with the plasma, and the role of thermal fluctuations in those interactions. We propose two different approaches to evaluate processes of electronic interactions in plasmas. To formulate the first approach we introduce modifications to the quantum-wave-packet dielectric method, which provides a reliable description over wide ranges of plasma densities and temperatures as compared with full quantum-mechanical dielectric theory. The second approach is a semiclassical dielectric method. It consists of including statistical quantum distributions and restrictions in the energy-loss expression, combined with the classical dielectric function for hot plasmas obtained from the linearized Vlasov-Poisson equation. We compare the results from both methods on an extensive range of parameters that include low, intermediate, and high energies, with densities and temperatures going from normal laboratory conditions to very high values, such as those of interest for studies on inertial fusion, Tokamak plasmas, and astrophysical media. We give also special consideration to the case of electrons, where the restrictions imposed by the identity with plasma electrons produce important effects.

The Formation of Astromolecule Ethynyl Cyclopropenylidene (c-C3HCCH) from C2H and c-C3H2

Abstract Reaction schema for the formation of the recently detected ethynyl cyclopropenylidene (c-C3HCCH) molecule are currently lacking in the literature. The present quantum chemical study shows that the reaction of the abundant ethynyl (C2H) and cyclopropenylidene (c-C3H2) molecules proceeds barrierlessly through the formation of a 1 2 A c-HC3HCCH intermediate at 71.2 kcal mol−1 below the reactants. The uphill exit channel climb for the C−H bond dissociation will compete with a transition state 45.9 kcal mol−1 below the reactants to form another, lower-energy intermediate ( 1 2 A ′ c-C3H2CCH) 84.3 kcal mol−1 below the reactants. The direct dissociation from the first intermediate is likely the dominant pathway under astrophysical conditions because the hydrogen leaving group can dissipate the energy kinetically. In either case of direct dissociation or crossing the transition state, the hydrogen atom dissociation to the final products lying 27.2 kcal mol−1 below the starting materials requires a crossover of electronic states with the singly occupied molecular orbital moving from the π cloud of the cyclopropenyl group onto the leaving H atom. As a result, this C2H + c-C3H2 → c-C3HCCH + H reaction should be as fast as theorized in astrophysical media such as TMC-1, where the titular molecule has now been observed.

Collisional excitation of NH by H2: Potential energy surface and scattering calculations.

Collisional data for the excitation of NH by H2 are key to accurately derive the NH abundance in astrophysical media. We present a new four-dimensional potential energy surface (PES) for the NH-H2 van der Waals complex. The ab initio calculations of the PES were carried out using the explicitly correlated partially spin-restricted coupled cluster method with single, double, and perturbative triple excitations [RCCSD(T)-F12a] with the augmented correlation-consistent polarized valence triple zeta basis set. The PES was represented by an angular expansion in terms of coupled spherical harmonics. The global minimum corresponds to the linear structure with a well depth De = 149.10 cm-1. The calculated dissociation energy D0 is found to be 30.55 and 22.11 cm-1 for ortho-H2 and para-H2 complexes, respectively. These results are in agreement with the experimental values. Then, we perform quantum close-coupling calculations of the fine structure resolved excitation cross sections of NH induced by collisions with ortho-H2 and para-H2 for collisional energies up to 500 cm-1. We find strong differences between collisions induced by ortho-H2 and para-H2. Propensity rules are discussed. The cross sections are larger for fine structure conserving transitions than for fine structure changing ones, as predicted by theory. These new results should help in interpreting NH interstellar spectra and better constrain the abundance of NH in interstellar molecular clouds.

Rotational (de-)excitation of oxophosphine (HPO) by collision with helium (He)

Three Dimensional Potential Energy Surface (3D-PES) of HPO-He in Jacobi coordinates is mapped. The new 3D-PES is performed at explicitly correlated Coupled Cluster level of theory with Single, Double and perturbative Triple excitation (CCSD(T)-F12a) related to aug-cc-pVTZ basis set. The computed PES is joined into quantum dynamical calculations to treat HPO nuclear motions, where HPO is considered as a rigid rotator colliding with He atom. Cross-sections for advances among the 29 lowest rotational levels of HPO (up to JKaKc = 808) are computed using quantum mechanical Close Coupling (CC) approach for total energy up to 900 cm−1. Rate coefficients relevant to HPO-He colliding system are deduced for [5–100] K temperature range. The present determination of rate coefficients will be useful in studies of HPO in astrophysical medium.

Thionitroxyl Radical (H2NS) Isomers: Structures, Vibrational Spectroscopy, Electronic States and Photochemistry

The thionitroxyl radical (H2NS) isomers are characterized using advanced ab initio methodologies. Computations are done using standard and explicitly correlated coupled cluster, CASSCF and MRCI approaches in conjunction with large basis sets, extrapolated to the complete basis set (CBS) limit. The lowest electronic states of different isomers are mapped along the stretching coordinates, thereby confirming the existence of the four already known ground state structures, namely H2NS, H2SN, cis-HNSH and trans-HNSH. Also, it is shown that only the lowest electronic excited states are stable, whereas the upper electronic states may undergo unimolecular decomposition processes forming H + HNS/HSN or the HN + SH or N + H2S or S + NH2 fragments. These data allow an assignment of the deep blue glow observed after reactions between “active nitrogen” and H2S at the beginning of the XXth century. For stable species, a set of accurate structural and spectroscopic parameters are provided. Since small nitrogen-sulfur molecular species are of astrophysical relevance, this work may help for identifying the thionitroxyl radical isomers in astrophysical media and in the laboratory.

Collisional (de-)excitation of protonated cyanoacetylene (HC3NH+) by helium at low and moderate temperatures

ABSTRACT Protonated cyanoacetylene, HC3NH+, is detected in astrophysical media, where it plays a key role as an intermediate in the chemistries of HCN/HNC and of cyanopolyynes. We first generated a potential energy surface (PES) describing the intermonomer interaction between HC3NH+ and He in Jacobi coordinates using the highly correlated CCSD(T)-F12/aug-cc-pVTZ ab initio methodology. Then, scattering calculations based on an exact close-coupling quantum-scattering technique were done to obtain pure rotational cross-sections for the rotational (de-)excitation of HC3NH+ after collision with He for total energies up to 2500 cm−1. These cross-sections are used to deduce the collision rates in the 5–350 K temperature range for the low-lying rotational levels of HC3NH+ (up to $j\,\, = \,\,15$). In addition, we generated an average PES for the HC3NH+–H2 system. The preliminary results show that the H2($j_{\mathrm{H_2}} = 0$) and He state-to-state de-excitation cross-sections have similar magnitudes, even though the H2 cross-sections are larger by a factor of 2–2.5. This work should help with the accurate derivation of protonated cyanoacetylene abundances in non-local thermodynamical equilibrium astrophysical media. These will put more constraints on the chemical pathways involving the formation and destruction of HC3NH+ while going back to the cyanopolyyne family and more generally those parts of nitrogen-containing molecular chemistry.

Sodium isocyanide–Helium potential energy surface and astrophysical applications

In this work, we generated the two-dimensional potential energy surface (2D-PES) of the l-NaNC–He van der Waals interacting system. The electronic computations are done at the CCSD(T)-F12/aug-cc-pVTZ level. This 2D-PES exhibits a unique shallow minimum for helium approaching l-NaNC from the Na atom side. Afterward, we derived an analytical form for this ab initio 2D-PES, which is incorporated into quantum scattering code to compute the rotational (de-)excitation cross sections (rate coefficients) of l-NaNC by collision with He atom for total energies up to 2000 cm−1 (from 5 to 300 K). The propensity rules that favor Δj = − 1 transitions are less pronounced than in the case of t-NaCN isomer. Our data may be used for the determination of the abundances, in astrophysical media, of the candidate isomer l-NaNC with respect to those of the already detected t-NaCN isomer. We also performed comparison with the astrophysical relevant Al- and Mg-bearing (iso)cyanide systems interacting with He.

Yebes 40 m radio telescope and the broad band NANOCOSMOS receivers at 7 mm and 3 mm for line surveys.

Yebes 40m radio telescope is the main and largest observing instrument at Yebes Observatory and it is devoted to Very Long Baseline Interferometry (VLBI) and single dish observations since 2010. It has been covering frequency bands between 2 GHz and 90 GHz in discontinuous and narrow windows in most of the cases, to match the current needs of the European VLBI Network (EVN) and the Global Millimeter VLBI Array (GMVA). Nanocosmos project, a European Union funded synergy grant, opened the possibility to increase the instantaneous frequency coverage to observe many molecular transitions with single tunnings in single dish mode. This reduces the observing time and maximises the output from the telescope. We present the technical specifications of the recently installed 31.5 - 50GHz (Q band) and 72 - 90.5 GHz (W band) receivers along with the main characteristics of the telescope at these frequency ranges. We have observed IRC+10216, CRL 2688 and CRL 618, which harbour a rich molecular chemistry, to demonstrate the capabilities of the new instrumentation for spectral observations in single dish mode. The results show the high sensitivity of the telescope in the Q band. The spectrum of IRC+10126 offers a signal to noise ratio never seen before for this source in this band. On the other hand, the spectrum normalised by the continuum flux towards CRL 618 in the W band demonstrates that the 40 m radio telescope produces comparable results to those from the IRAM 30 m radio telescope, although with a smaller sensitivity. The new receivers fulfil one of the main goals of Nanocosmos and open the possibility to study the spectrum of different astrophysical media with unprecedented sensitivity.

Neutral and Multicharged Ions of Small Aluminum Oxides: Structures, Spectroscopy, and Energetics.

We use accurate ab initio methodologies at the Coupled Cluster level to compute the stable forms of AlxOyq+ (x = 1, 2; y = 1, 2; q = 0-3) species for which we derive an accurate set of geometrical and vibrational spectroscopic data. We also determine their adiabatic single, double, and triple ionization energies. These spectroscopic and thermodynamical data may help for identifying these species in laboratory, in astrophysical media, and in plasma and confirm previous observations of multi-charged AlxOy clusters by Atom Probe Tomography (ATP) coupled to mass spectrometry. They should help for identifying and understanding the complex chemical processes occurring during the Al2O3 growth in laboratory and in astrophysical media and those taking place at the degradation of Al-containing materials by high temperature corrosion/oxidation.

Characterization of the simplest sulfenyl thiocyanate: isomers, spectroscopy and implications of astrophysical and biological relevance.

Sulfenyl thiocyanate compounds, RSSCN, are involved in the human immune system biochemical processes. They are also the routes for the synthesis of complex S-containing species such as polypeptides, or symmetrical (RSSR) and unsymmetrical disulfides (RSSR'). At present, we have characterized the stable forms of the simplest sulfenyl thiocyanate compound, HSSCN, at the coupled cluster level. We found twenty-three isomers, for which we determined a set of structural parameters, anharmonic frequencies and reaction energies for the formation of the corresponding diatomic + triatomic and atomic + tetratomic fragments. We also discussed the implications of the present findings for biological entities containing a disulfide bridge, where we identified three isomers that may serve as prototypes. Similarities and differences with other S/N hybrid bioactive molecules are also discussed. From an astrophysical point of view, we expect HSSCN isomers to be present in astrophysical media, since several of their molecular fragments have already been detected. In sum, the present set of data can be used for the identification of HSSCN compounds and understanding the physical chemistry of sulfur containing molecules in vivo, in the laboratory and in astrophysical media.

On sampling of scattering phase functions

Abstract Monte Carlo radiative transfer, which has been demonstrated as a successful algorithm for modelling radiation transport through the astrophysical medium, relies on sampling of scattering phase functions. We review several classic sampling algorithms such as the tabulated method and the accept–reject method for sampling the scattering phase function. The tabulated method uses a piecewise constant approximation for the true scattering phase function; we improve its sampling performance on a small scattering angle by using piecewise linear and piecewise log-linear approximations. It has previously been believed that certain complicated analytic phase functions such as the Fournier–Forand phase function cannot be simulated without approximations. We show that the tabulated method combined with the accept–reject method can be applied to sample such complicated scattering phase functions accurately. Furthermore, we introduce the Gibbs sampling method for sampling complicated approximate analytic phase functions. In addition, we propose a new modified Henyey–Greenstein phase function with exponential decay terms for modelling realistic dust scattering. Based on Monte Carlo simulations of radiative transfer through a plane-parallel medium, we also demonstrate that the result simulated with the new phase function can provide a good fit to the result simulated with the realistic dust phase function.

Collision excitation of sodium cyanide molecule by helium at low temperature

ABSTRACT Cyanides/isocyanides are the most common metal-containing molecules in interstellar medium. In this work, quantum scattering calculations were carried out to determine the rotational (de-)excitation cross-sections of the most stable form of the sodium cyanide molecule, t-NaCN, in collision with the helium atom. Rate coefficients for the first 43 rotational levels (up to ${j_{{K_a}{K_c}}}$ = 63,3) of NaCN were determined for kinetic temperatures ranging from 1 to 30 K. Prior to that, we constructed a new three-dimensional potential energy surface (3D-PES) for the t-NaCN–He interacting system. These electronic structure computations are done at the CCSD(T)-F12/aug-cc-pVTZ level of theory. Computations show the dominance of Δj = ΔKc = −1 transitions, which is related to the dissymmetric shape of the t-NaCN–He 3D-PES. The NaCN–He rate coefficients are of the same order of magnitude (∼10−11 cm3.s−1) as those of other metal CN-containing molecules such as MgCN and AlCN in collision with He. This work is a contribution for understanding and modelling the abundances and chemistry of nitriles in astrophysical media.