Search

To facilitate atmospheric and spectroscopic studies of carbon disulfide, or CS _2 , in both planetary and exoplanetary atmospheres, we adopt the “Best Theory + Reliable High-resolution Experiment” algorithm to generate semiempirical IR line lists for the 20 most abundant CS _2 isotopologues, denoted as Ames-296K. The IR lists are computed using the Ames-1 potential energy surface, refined using the experimental transition set and an ab initio dipole moment surface fitted from CCSD(T)/aug-cc-pV(T/Q/5+d)Z dipoles extrapolated to a one-particle basis set limit. The IR lists cover the range of 0–10,000 cm ^−1 , with an S _296K cutoff at 10 ^−31 cm ^−1 /molecule·cm ^−2 (abundance included). A “natural” IR line list at 296 K includes about 10 million lines of the 20 isotopologues, with their intensities scaled by the corresponding abundances. The zero-point energy, partition functions, and abundances are reported for each isotopologue. The energy levels in the global effective Hamiltonian model for ^12 C ^32 S _2 are adopted to improve the line position accuracy. This new IR list for the main isotopologue is denoted as A+I.296K. Reliable HITRAN2020 line positions are also utilized to improve the accuracy of the ^32 S ^12 C ^34 S, ^32 S ^12 C ^33 S, and ^32 S ^13 C ^32 S isotopologue line lists. The final composite line list is validated against Pacific Northwest National Laboratory experimental cross sections, showing excellent agreement. The agreement supports the quality of the composite line list and the power of synergy between experiment and theory. The new data are proposed for use in updating and expanding the CS _2 data in HITRAN and other high-resolution IR databases. Supplementary files are available in Zenodo and AHED.

We present the first high spectral resolution mid-infrared survey in the Orion BN/KL region, covering 7.2–28.3 μ m. With SOFIA/EXES, we target the enigmatic source Orion IRc2. While this is in the most prolifically studied massive star-forming region, longer wavelengths and molecular emission lines dominated previous spectral surveys. The mid-infrared observations in this work access different components and molecular species in unprecedented detail. We unambiguously identify two new kinematic components, both chemically rich with multiple molecular absorption lines. The “blue clump” has v _LSR = −7.1 ± 0.7 km s ^−1 , and the “red clump” has 1.4 ± 0.5 km s ^−1 . While the blue and red clumps have similar temperatures and line widths, molecular species in the blue clump have higher column densities. They are both likely linked to pure rotational H _2 emission also covered by this survey. This work provides evidence for the scenario that the blue and red clumps are distinct components unrelated to the classic components in the Orion BN/KL region. Comparison to spectroscopic surveys toward other infrared targets in the region show that the blue clump is clearly extended. We analyze, compare, and present in-depth findings on the physical conditions of C _2 H _2 , ^13 CCH _2 , CH _4 , CS, H _2 O, HCN, ${{\rm{H}}}^{13}\mathrm{CN}$ , HNC, NH _3 , and SO _2 absorption lines and an H _2 emission line associated with the blue and red clumps. We also provide limited analysis of H _2 O and SiO molecular emission lines toward Orion IRc2 and the atomic forbidden transitions [Fe ii ], [S i ], [S iii ], and [Ne ii ].

It has been shown that rotational lines observed in the Horsehead nebula photodissociation region (PDR) are probably not caused by l-C3H+, as was originally suggested. In the search for viable alternative candidate carriers, quartic force fields are employed here to provide highly accurate rotational constants, as well as fundamental vibrational frequencies, for another candidate carrier: 1 1 A' C3H-. The ab initio computed spectroscopic constants provided in this work are, compared to those necessary to define the observed lines, as accurate as the computed spectroscopic constants for many of the known interstellar anions. Additionally, the computed Deff for C3H- is three times closer to the D deduced from the observed Horsehead nebula lines relative to l-C3H+. As a result, 1 1 A' C3H- is a more viable candidate for these observed rotational transitions. It has been previously proposed that at least C6H- may be present in the Horsehead nebular PDR formed by way of radiative attachment through its dipole-bound excited state. C3H- could form in a similar way through its dipole-bound state, but its valence excited state increases the number of relaxation pathways possible to reach the ground electronic state. In turn, the rate of formation for C3H- could be greater than the rate of its destruction. C3H- would be the seventh confirmed interstellar anion detected within the past decade and the first CnH- molecular anion with an odd n. [ABSTRACT FROM AUTHOR]

Recently, we reported ab initio quartic force fields (QFFs) for the cyclic and linear forms of the Due to image rights restrictions, multiple line equation(s) cannot be graphically displayed molecular cation, referred to as Due to image rights restrictions, multiple line equation(s) cannot be graphically displayed. Specifically the singles and doubles coupled-cluster method that includes a perturbational estimate of connected triple excitations, CCSD(T), was used in conjunction with extrapolation to the one-particle basis set limit, and corrections for scalar relativity and core correlation were included. In the present study, we use these QFFs to compute highly accurate fundamental vibrational frequencies and other spectroscopic constants for the Due to image rights restrictions, multiple line equation(s) cannot be graphically displayed. isotoplogues of Due to image rights restrictions, multiple line equation(s) cannot be graphically displayed., and the H2CCCD+, HDCCCH+, H213CCCH+, H2C 13CCH+, and H2CC13CH+ isotopologues of Due to image rights restrictions, multiple line equation(s) cannot be graphically displayed. Improvements in ab intitio methods have now made it possible to identify small molecules in an astronomical observation without the aid of high-resolution experimental data. We also report dipole moment values and show that the above-mentioned cyclic isotopologues have values of 0.094, 0.225, and 0.312 D, respectively, while the Due to image rights restrictions, multiple line equation(s) cannot be graphically displayed. isotopologues have values that range between 0.325 and 0.811 D. Thus, it is hoped that the highly accurate spectroscopic constants and data provided herein for the 13C and deuterium isotopologues of the cyclic and linear forms of Due to image rights restrictions, multiple line equation(s) cannot be graphically displayed. will enable their identification in astronomical observations from the Herschel Space Observatory the Stratospheric Observatory for Infrared Astronomy, the Atacama Large Millimeter Array, and in the future, the James Webb Space Telescope. [ABSTRACT FROM AUTHOR]

We present high spectral resolution observations from 12.96 to 13.33 microns toward Orion IRc2 using the mid-infrared spectrograph, Echelon-Cross-Echelle Spectrograph (EXES), at Stratospheric Observatory for Infrared Astronomy (SOFIA). These observations probe the physical and chemical conditions of the Orion hot core, which is sampled by a bright, compact, mid-infrared background continuum source in the region, IRc2. All 10 of the rovibrational C2H2 transitions expected in our spectral coverage are detected with high signal-to-noise ratios (S/Ns), yielding continuous coverage of the R-branch lines from J = 9–8 to J = 18–17, including both ortho and para species. Eight of these rovibrational transitions are newly reported detections. The isotopologue, 13CCH2, is clearly detected with a high S/N. This enabled a direct measurement of the 12C/13C isotopic ratio for the Orion hot core of 14 ± 1 and an estimated maximum value of 21. We also detected several HCN rovibrational lines. The ortho and para C2H2 ladders are clearly separate, and tracing two different temperatures, 226 K and 164 K, respectively, with a non-equilibrium ortho to para ratio (OPR) of 1.7 ± 0.1. Additionally, the ortho and para VLSR values differ by about 1.8 ± 0.2 km s−1, while the mean line widths differ by 0.7 ± 0.2 km s−1, suggesting that these species are not uniformly mixed along the line of sight to IRc2. We propose that the abnormally low C2H2 OPR could be a remnant from an earlier, colder phase, before the density enhancement (now the hot core) was impacted by shocks generated from an explosive event 500 years ago. [ABSTRACT FROM AUTHOR]

In this work we report on high-resolution IR absorption studies that provide a detailed view on how the peripheral structure of irregular polycyclic aromatic hydrocarbons (PAHs) affects the shape and position of their 3 μm absorption band. For this purpose, we present mass-selected, high-resolution absorption spectra of cold and isolated phenanthrene, pyrene, benz[a]antracene, chrysene, triphenylene, and perylene molecules in the 2950–3150 cm−1 range. The experimental spectra are compared with standard harmonic calculations and anharmonic calculations using a modified version of the SPECTRO program that incorporates a Fermi resonance treatment utilizing intensity redistribution. We show that the 3 μm region is dominated by the effects of anharmonicity, resulting in many more bands than would have been expected in a purely harmonic approximation. Importantly, we find that anharmonic spectra as calculated by SPECTRO are in good agreement with the experimental spectra. Together with previously reported high-resolution spectra of linear acenes, the present spectra provide us with an extensive data set of spectra of PAHs with a varying number of aromatic rings, with geometries that range from open to highly condensed structures, and featuring CH groups in all possible edge configurations. We discuss the astrophysical implications of the comparison of these spectra on the interpretation of the appearance of the aromatic infrared 3 μm band, and on features such as the two-component emission character of this band and the 3 μm emission plateau. [ABSTRACT FROM AUTHOR]

A correction to the article "High-Resolution IR Absorption Spectroscopy of Polycyclic Aromatic Hydrocarbons: The Realm of Anharmonicity" that was published in the previous issue, is presented.

We report on an experimental and theoretical investigation of the importance of anharmonicity in the 3-μm CH stretching region of polycyclic aromatic hydrocarbon (PAH) molecules. We present mass-resolved, high-resolution spectra of the gas-phase cold (∼4 K) linear PAH molecules naphthalene, anthracene, and tetracene. The measured IR spectra show a surprisingly high number of strong vibrational bands. For naphthalene, the observed bands are well separated and limited by the rotational contour, revealing the band symmetries. Comparisons are made to the harmonic and anharmonic approaches of the widely used Gaussian software. We also present calculated spectra of these acenes using the computational program SPECTRO, providing anharmonic predictions with a Fermi-resonance treatment that utilizes intensity redistribution. We demonstrate that the anharmonicity of the investigated acenes is strong, dominated by Fermi resonances between the fundamental and double combination modes, with triple combination bands as possible candidates to resolve remaining discrepancies. The anharmonic spectra as calculated with SPECTRO lead to predictions of the main bands that fall within 0.5% of the experimental frequencies. The implications for the aromatic infrared bands, specifically the 3-μm band, are discussed. [ABSTRACT FROM AUTHOR]