Laboratory spectroscopic study of isotopic thioformaldehyde, H<sub>2</sub>CS, and determination of its equilibrium structure

Müller, H. S. P.; Maeda, Atsuko; Thorwirth, Sven; Lewen, Frank; Schlemmer, Stephan; Medvedev, Ivan R.; Winnewisser, M.; Lucia, Frank C. De; Herbst, Eric

doi:10.1051/0004-6361/201834517

Cited by 37 publications

(31 citation statements)

References 72 publications

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“…The advantage of taking i into account explicitly is that rotational parameters of isotopic species to be studied can be estimated much more accurately, in particular for atoms with more than two isotopes or for multiply substituted isotopologs (Epple & Rudolph 1992;Müller & Gerry 1994;Müller et al 2019), if residuals of known isotopologs can be transferred to the values of the desired isotopolog. In the case of H 2 CS, Müller et al (2019) extrapolated the residuals of H 2 C 32 S, H 2 C 33 S, and H 2 C 34 S to H 2 C 36 S, and those of H 2 C 32 S, H 2 C 34 S, and H 13 2 CS to H 13 2 C 34 S. The equilibrium (or r e ) structure of a molecule in the potential minimum is the most meaningful structure. However, it is also the most elusive structure because data of more than one isotopolog are needed for molecules with three or more Table 4.…”

Section: Structural Parameters Of Cyclopropenonementioning

confidence: 99%

“…Scaling of quantum-chemically derived distortion parameters should be better than scaling by appropriate powers of the ratios of 2A − B − C, B + C, and B − C, as done, for example, in the recent case of isotopic H 2 CS (Müller et al 2019). This type of scaling usually works quite well for heavy-atom substitutions, but less so for H to D substitutions, in particular for molecules with few atoms.…”

Section: Spectroscopic Parametersmentioning

confidence: 99%

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Rotational spectroscopy of isotopic cyclopropenone, c-H₂C₃O, and determination of its equilibrium structure

Müller

Brahmi

Guillemin

et al. 2021

A&A

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Context. Cyclopropenone was first detected in the cold and less dense envelope of the giant molecular cloud 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. Aims. We aim to extend existing line lists of isotopologs of c-H 2 C 3 O 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. Methods. We employed a cyclopropenone sample in natural isotopic composition to investigate the rotational spectra of the main and 18 O-containing isotopologs as well as the two isotopomers containing one 13 C 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. Results. We determined new or improved spectroscopic parameters for six isotopologs and structural parameters according to different structure models. Conclusions. 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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Section: Structural Parameters Of Cyclopropenonementioning

confidence: 99%

Section: Spectroscopic Parametersmentioning

confidence: 99%

Rotational spectroscopy of isotopic cyclopropenone, c-H₂C₃O, and determination of its equilibrium structure

Müller

Brahmi

Guillemin

et al. 2021

A&A

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“…This strategy has been pioneered by the work of Pulay, Meyer, and Boggs about 40 years ago. 14 Its accuracy has been carefully established, 15 and it can nowadays be applied almost routinely (e.g., see ref (16)).…”

Section: Introductionmentioning

confidence: 99%

Equilibrium Structures of the Phosphorus Trihalides PF₃ and PCl₃, and the Phosphoranes PH₃F₂, PF₅, PCl₃F₂, and PCl₅

Breidung

Thiel

2019

J. Phys. Chem. A

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Among the title species, a reliable and accurate equilibrium geometry (re structure) is available only for PF3, which has been determined experimentally more than 20 years ago. Here, we report accurate re structures for all title molecules, which were obtained using a composite computational approach based on explicitly correlated coupled-cluster theory (CCSD(T)-F12b) in conjunction with a large correlation-consistent basis set (cc-pCVQZ-F12) to take core–valence electron correlation into account. Additional terms were included to correct for the effects of iterative triple excitations (CCSDT), noniterative quadruple excitations (CCSDT(Q)), and scalar relativistic contributions (DKH2-CCSD(T)). The performance of this computational procedure was established through test calculations on selected small molecules (PH, PF, PCl, PH2, PF2, and PH3). For PF3, PCl3, PH3F2, and PF5 sufficiently accurate experimental ground-state rotational constants from the literature were used to determine semiexperimental re structures, which were found to be in excellent agreement with the corresponding best estimates from the current composite approach. The recommended equilibrium structural parameters are for PCl3, re(PCl) = 203.94 pm and θe(ClPCl) = 100.18°; for PH3F2, re(PHeq) = 138.38 pm and re(PFax) = 164.15 pm; for PF5, re(PFeq) = 153.10 pm and re(PFax) = 157.14 pm; for PCl3F2, re(PCleq) = 200.21 pm and re(PFax) = 159.37 pm; and for PCl5, re(PCleq) = 201.29 pm and re(PClax) = 211.83 pm. The associated uncertainties are estimated to be ±0.10 pm and ±0.10°, respectively.

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“…Further details on the spectrometer system are available elsewhere [44]. Accuracies of 10 kHz can be achieved with this spectrometer [49,50] but for the weak lines of 13 CH3SH in the present study, we attributed uncertainties of 100 kHz and 200 kHz.…”

Section: Methodsmentioning

confidence: 95%

Rotational spectrum of isotopic methyl mercaptan, ¹³CH₃SH, in the laboratory and towards Sagittarius B2(N2)

et al. 2020

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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 to provide accurate spectroscopic parameters for the 13 CH3SH isotopologue to facilitate its identification 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 torsionrotation 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 52parameter 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 blendedwith emission from other species, which prevents us from identifying 13 CH3SH in this source.

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Laboratory spectroscopic study of isotopic thioformaldehyde, H₂CS, and determination of its equilibrium structure

Cited by 37 publications

References 72 publications

Rotational spectroscopy of isotopic cyclopropenone, c-H₂C₃O, and determination of its equilibrium structure

Rotational spectroscopy of isotopic cyclopropenone, c-H₂C₃O, and determination of its equilibrium structure

Equilibrium Structures of the Phosphorus Trihalides PF₃ and PCl₃, and the Phosphoranes PH₃F₂, PF₅, PCl₃F₂, and PCl₅

Rotational spectrum of isotopic methyl mercaptan, ¹³CH₃SH, in the laboratory and towards Sagittarius B2(N2)

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Laboratory spectroscopic study of isotopic thioformaldehyde, H2CS, and determination of its equilibrium structure

Cited by 37 publications

References 72 publications

Rotational spectroscopy of isotopic cyclopropenone, c-H2C3O, and determination of its equilibrium structure

Rotational spectroscopy of isotopic cyclopropenone, c-H2C3O, and determination of its equilibrium structure

Equilibrium Structures of the Phosphorus Trihalides PF3 and PCl3, and the Phosphoranes PH3F2, PF5, PCl3F2, and PCl5

Rotational spectrum of isotopic methyl mercaptan, 13CH3SH, in the laboratory and towards Sagittarius B2(N2)

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Laboratory spectroscopic study of isotopic thioformaldehyde, H₂CS, and determination of its equilibrium structure

Rotational spectroscopy of isotopic cyclopropenone, c-H₂C₃O, and determination of its equilibrium structure

Rotational spectroscopy of isotopic cyclopropenone, c-H₂C₃O, and determination of its equilibrium structure

Equilibrium Structures of the Phosphorus Trihalides PF₃ and PCl₃, and the Phosphoranes PH₃F₂, PF₅, PCl₃F₂, and PCl₅

Rotational spectrum of isotopic methyl mercaptan, ¹³CH₃SH, in the laboratory and towards Sagittarius B2(N2)