Theoretical rovibrational characterization of the cis/trans-HCSH and H2SC isomers of the known interstellar molecule thioformaldehyde

Inostroza-Pino, Natalia; Palmer, C. Zachary; Lee, Timothy J.; Fortenberry, Ryan C.

doi:10.1016/j.jms.2020.111273

Cited by 13 publications

(8 citation statements)

References 74 publications

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“…It will also build upon previous work for similar data in AlOH and will utilize the benchmarked comparisons of AlOH theoretical data to experiment in order to provide more refined insights into OAlOH. The methods employed have previously been shown to produce vibrational frequencies to within 5 cm –1 or better of gas-phase experiment in many cases − and within an average of 20 MHz for the B and C rotational constants of tetraatomic and larger, closed-shell molecules . Consequently, this work will provide the data necessary for observation of OAlOH in the laboratory and may even inform radioastronomical or infrared (via the Stratospheric Observatory for Infrared Astronomy or the upcoming James Webb Space Telescope, JWST ) searches for it in the ISM.…”

Section: Introductionmentioning

confidence: 87%

Anharmonic Frequencies and Spectroscopic Constants of OAlOH and AlOH: Strong Bonding but Unhindered Motion

2020

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The astrophysical buildup of premineral nanocrystals from atoms to the smallest network-covalent solids will require observations of various small molecules containing the most common elements in minerals including aluminum and oxygen. The present work utilizes high-level quantum chemical quartic force field (QFF) approaches to produce anharmonic vibrational frequencies and spectroscopic constants for such species. The computed B eff for the astrochemically known AlOH molecule at 15780.5 MHz is a mere 40 MHz above the experimental value implying that the B eff for OAlOH at 5580.9 MHz is similarly accurate. The additional 7.31 D dipole moment in OAlOH implies that this molecule is a viable target for interstellar observation. Unlike the other anharmonic vibrational frequencies reported in this work, the Al−O−H bending frequencies in both AlOH and OAlOH are poorly described in the present QFF results. However, this failing actually highlights the fact that these bends are exceptionally floppy yet with counterintuitive exceedingly strong bonding. The Al−O bond energies are 128.2 and 107.2 kcal/mol, respective of AlOH and OAlOH, while the barriers to linearity are meager 16.6 and 380.7 cm −1 (0.1 and 1.1 kcal/mol).

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Section: Introductionmentioning

confidence: 87%

Anharmonic Frequencies and Spectroscopic Constants of OAlOH and AlOH: Strong Bonding but Unhindered Motion

2020

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“…Species of potential interest include stable compounds of the light noble gases, 29 ions whose absorption spectra have so far been measured only in neon or argon matrices, 2 or labile organic ions that are important intermediates in atmospheric extraterrestrial chemistry. 30 , 31 …”

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confidence: 99%

“…Furthermore, they suggest that our experimental approach may be used to stabilize any transient molecular ion AB ± provided its binding energy A-B ± exceeds its binding energy with helium. Species of potential interest include stable compounds of the light noble gases, ions whose absorption spectra have so far been measured only in neon or argon matrices, or labile organic ions that are important intermediates in atmospheric extraterrestrial chemistry. , …”

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confidence: 99%

SF₆⁺: Stabilizing Transient Ions in Helium Nanodroplets

Albertini

Bergmeister

Laimer

et al. 2021

J. Phys. Chem. Lett.

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There are myriad ions that are deemed too short-lived to be experimentally accessible. One of them is SF 6 + . It has never been observed, although not for lack of trying. We demonstrate that long-lived SF 6 + can be formed by doping charged helium nanodroplets (HNDs) with sulfur hexafluoride; excess helium is then gently stripped from the doped HNDs by collisions with helium gas. The ion is identified by high-resolution mass spectrometry (resolution m /Δ m = 15000), the close agreement between the expected and observed yield of ions that contain minor sulfur isotopes, and collision-induced dissociation in which mass-selected He n SF 6 + ions collide with helium gas. Under optimized conditions, the yield of SF 6 + exceeds that of SF 5 + . The procedure is versatile and suitable for stabilizing many other transient molecular ions.

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“…The simple–internal coordinate system for HOOH requires 665 points for the QFF and is defined from the atoms in Figure 1 a [ 39 , 40 ]:

…”

Section: Computational Detailsmentioning

confidence: 99%

Spectral Signatures of Hydrogen Thioperoxide (HOSH) and Hydrogen Persulfide (HSSH): Possible Molecular Sulfur Sinks in the Dense ISM

2022

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For decades, sulfur has remained underdetected in molecular form within the dense interstellar medium (ISM), and somewhere a molecular sulfur sink exists where it may be hiding. With the discovery of hydrogen peroxide (HOOH) in the ISM in 2011, a natural starting point may be found in sulfur-bearing analogs that are chemically similar to HOOH: hydrogen thioperoxide (HOSH) and hydrogen persulfide (HSSH). The present theoretical study couples the accuracy in the anharmonic fundamental vibrational frequencies from the explicitly correlated coupled cluster theory with the accurate rotational constants provided by canonical high-level coupled cluster theory to produce rovibrational spectra for use in the potential observation of HOSH and HSSH. The ν6 mode for HSSH at 886.1 cm−1 is within 0.2 cm−1 of the gas-phase experiment, and the B0 rotational constant for HSSH of 6979.5 MHz is within 9.0 MHz of the experimental benchmarks, implying that the unknown spectral features (such as the first overtones and combination bands) provided herein are similarly accurate. Notably, a previous experimentally-attributed 2ν1 mode, at 7041.8 cm−1, has been reassigned to the ν1+ν5 combination band based on the present work’s ν1+ν5 value at 7034.3 cm−1. The most intense vibrational transitions for each molecule are the torsions, with HOSH having a more intense transition of 72 km/mol compared to HSSH’s intensity of 14 km/mol. Furthermore, HOSH has a larger net dipole moment of 1.60 D compared to HSSH’s 1.15 D. While HOSH may be the more likely candidate of the two for possible astronomical observation via vibrational spectroscopy due to the notable difference in their intensities, both HSSH and HOSH have large enough net dipole moments to be detectable by rotational spectroscopy to discover the role these molecules may have as possible molecular sulfur sinks in the dense ISM.

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Theoretical rovibrational characterization of the cis/trans-HCSH and H2SC isomers of the known interstellar molecule thioformaldehyde

Cited by 13 publications

References 74 publications

Anharmonic Frequencies and Spectroscopic Constants of OAlOH and AlOH: Strong Bonding but Unhindered Motion

Anharmonic Frequencies and Spectroscopic Constants of OAlOH and AlOH: Strong Bonding but Unhindered Motion

SF₆⁺: Stabilizing Transient Ions in Helium Nanodroplets

Spectral Signatures of Hydrogen Thioperoxide (HOSH) and Hydrogen Persulfide (HSSH): Possible Molecular Sulfur Sinks in the Dense ISM

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Theoretical rovibrational characterization of the cis/trans-HCSH and H2SC isomers of the known interstellar molecule thioformaldehyde

Cited by 13 publications

References 74 publications

Anharmonic Frequencies and Spectroscopic Constants of OAlOH and AlOH: Strong Bonding but Unhindered Motion

Anharmonic Frequencies and Spectroscopic Constants of OAlOH and AlOH: Strong Bonding but Unhindered Motion

SF6+: Stabilizing Transient Ions in Helium Nanodroplets

Spectral Signatures of Hydrogen Thioperoxide (HOSH) and Hydrogen Persulfide (HSSH): Possible Molecular Sulfur Sinks in the Dense ISM

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SF₆⁺: Stabilizing Transient Ions in Helium Nanodroplets