Internal rotation and framework relaxation in ethene thiol

Almond, V.; Permanand, R. R.; Macdonald, John N.

doi:10.1016/0022-2860(85)85009-2

Cited by 39 publications

(28 citation statements)

References 20 publications

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“…The sulfur analogues [C 2 ,H 4 ,S] on the other hand are near-isoenergetic at the current level of treatment: with the exception of CH 3 CHS, the three remaining isomers are within ∼0.5 kJ/mol of one another, with anti-vinyl mercaptan being the highest in energy (5.3 kJ/mol). Our ab initio energy difference between the vinyl mercaptan isomers (0.5 kJ/mol) is in quantitative agreement with the estimate by Almond et al (1985) (0.6 kJ/mol).…”

Section: Computational Detailssupporting

confidence: 89%

“…Photoelectron (Chin et al 1994) and low-resolution vibrational spectra (Almond et al 1977(Almond et al , 1983 have been reported, while pure rotational spectra of the two isomers in the ground and several excited vibrational states have only been measured up to 50 GHz (Almond et al 1977;Tanimoto & Saito 1977;. Isotopic investigations of the microwave spectra of the SD isotopologues 1 (Tanimoto & Saito 1977;, and extensive studies of deuterated variants of the syn isomer (Almond et al 1985) that followed, enabled a determination of a partial geometry; owing to the absence of experimental data for isotopic species involving substitution at any of the three heavy atoms, a complete structure has not been reported. Additionally, accurate dipole moments in the ground vibrational state are available from Stark measurements: µ a = 0.813(1) D, µ b = 0.376(4) D, µ tot = 0.896(3) D for the syn isomer; and µ a = 0.425(10) D, µ b = 1.033(10) D, µ tot = 1.117(14) D for the anti one .…”

Section: Syn Antimentioning

confidence: 99%

“…Vinyl mercaptan exists in the gas phase in two distinct rotameric forms, the planar syn and quasi-planar anti isomers (Fig. 1), with the former only slightly more stable than the latter by about 0.6 kJ/mol (Almond et al 1983(Almond et al , 1985Plant et al 1992), which yields a syn/anti ratio at room temperature of about 1.2. It is worth noting that while the equilibrium structure of the anti isomer is non-planar, with a calculated SH torsional angle of about 130-150 • , the barrier to linearity (0.14 kJ/mol) is small compared to the zero-point vibration, which results in a vibrationally-averaged planar structure Almond et al 1985).…”

Section: Introductionmentioning

confidence: 99%

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Submillimeter spectroscopy and astronomical searches of vinyl mercaptan, C₂H₃SH

Martin‐Drumel

Lee

Беллоче

et al. 2019

A&A

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Context. New laboratory investigations of the rotational spectrum of postulated astronomical species are essential to support the assignment and analysis of current astronomical surveys. In particular, considerable interest surrounds sulfur analogs of oxygencontaining interstellar molecules and their isomers. Aims. To enable reliable interstellar searches of vinyl mercaptan, the sulfur-containing analog to the astronomical species vinyl alcohol, we have investigated its pure rotational spectrum at millimeter wavelengths. Methods. We have extended the pure rotational investigation of the two isomers syn and anti vinyl mercaptan to the millimeter domain using a frequency-multiplication spectrometer. The species were produced by a radiofrequency discharge in 1,2-ethanedithiol. Additional transitions have been re-measured in the centimeter band using Fourier-transform microwave spectroscopy to better determine rest frequencies of transitions with low-J and low-K a values. Experimental investigations were supported by quantum chemical calculations on the energetics of both the [C 2 ,H 4 ,S] and [C 2 ,H 4 ,O] isomeric families. Interstellar searches for both syn and anti vinyl mercaptan as well as vinyl alcohol were performed in the EMoCA (Exploring Molecular Complexity with ALMA) spectral line survey carried out toward Sagittarius (Sgr) B2(N2) with the Atacama Large Millimeter/submillimeter Array (ALMA). Results. Highly accurate experimental frequencies (to better than 100 kHz accuracy) for both syn and anti isomers of vinyl mercaptan have been measured up to 250 GHz; these deviate considerably from predictions based on extrapolation of previous microwave measurements. Reliable frequency predictions of the astronomically most interesting millimeter-wave lines for these two species can now be derived from the best-fit spectroscopic constants. From the energetic investigations, the four lowest singlet isomers of the [C 2 ,H 4 ,S] family are calculated to be nearly isoenergetic, which makes this family a fairly unique test bed for assessing possible reaction pathways. Upper limits for the column density of syn and anti vinyl mercaptan are derived toward the extremely molecule-rich star-forming region Sgr B2(N2) enabling comparison with selected complex organic molecules.

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Section: Computational Detailssupporting

confidence: 89%

Section: Syn Antimentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Submillimeter spectroscopy and astronomical searches of vinyl mercaptan, C₂H₃SH

Martin‐Drumel

Lee

Беллоче

et al. 2019

A&A

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show abstract

“…The eigenvalues and eigenvectors for the vibrational mode were computed by standard procedures. 1,10,11 Wavepackets on a periodic potential Wavepackets W(a,t) were constructed of the form,…”

Section: Computational Approachmentioning

confidence: 99%

“…(5), rather than by a set of state vectors each present with di †erent probabilities.1,8,13 For such a Boltzmann wavepacket, the energy, SET, is the average contribution of the relevant vibrational mode to the energy of the ensemble, eqn. (11).…”

Section: Computational Approachmentioning

confidence: 99%