A theoretical study on the spectroscopy, structure, and stability of C2H3NS molecules

Gronowski, Marcin; Turowski, Michał; Custer, Thomas; Kołos, Robert

doi:10.1007/s00214-016-1978-6

Cited by 5 publications

(13 citation statements)

References 70 publications

(86 reference statements)

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“…Theoretical IR frequencies, intensities, and rotational constants for mercaptoacetonitrile (HS–CH 2 –CN) along with other C 2 H 3 SN isomers have been published previously . Only a comparison of predicted anharmonic IR frequencies for synclinal and antiperiplanar conformers, not provided in the previous work, are given here in Table .…”

Section: Resultsmentioning

confidence: 99%

“…Theoretical IR frequencies, intensities, and rotational constants for mercaptoacetonitrile (HS−CH 2 −CN) along with other C 2 H 3 SN isomers have been published previously. 1 Only a comparison of predicted anharmonic IR frequencies for synclinal and antiperiplanar conformers, not provided in the previous work, are given here in Table 1. Calculations similar to those performed for C 2 H 3 SN isomers were also performed for the C 2 H 2 NCl family of isomers, which includes Cl−CH 2 −CN (CAN).…”

Section: Resultsmentioning

confidence: 99%

“…Outside of these recent works, only a handful of studies on mercaptoacetonitrile are available in the literature. Several synthetic routes to its formation have been explored and routine 1 H and 13 C NMR as well as mass spectrometry and IR spectroscopy were used to characterize the products. 23−26 Most pertinent to the work at hand are spectroscopic measurements in the infrared and all reported spectra to date are for the pure liquid.…”

Section: Introductionmentioning

confidence: 99%

“…Theoretical studies 1 show that mercaptoacetonitrile (HS− CH 2 −CN), methyl isothiocyanate (CH 3 NCS), and methyl thiocyanate (CH 3 SCN) are the three most stable molecules of the C 2 H 3 NS family, having energies of 0, 7.8, and 12.4 kJ/mol, respectively.…”

Section: Introductionmentioning

confidence: 99%

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Photochemistry of XCH₂CN (X = −Cl, −SH) in Argon Matrices

et al. 2019

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We report infrared spectra and photochemical behavior of the potentially astrochemically significant species, mercaptoacetonitrile (HS-CH 2 C≡N) and, for comparison purposes, chloroacetonitrile (Cl-CH 2 C≡N), both suspended in an argon matrix at 6K. Photolytic formation of the isocyano products HS-CH 2-NC and Cl-CH 2-NC were observed as well as CH 3 NSC and CH 3 SCN (in HS-CH 2 CN photolysis). While no dissociation products were observed for Cl-CH 2-CN, photolysis of HS-CH 2-CN produced compounds necessitating the loss of the CN group to form CH 2 =S, the SH group to form H 2 C-CN and HC-CN, or both CN and SH to form CH 3 and CH 4. Observation of emission spectra upon annealing indicates the presence of free sulfur atom in matrices of photolyzed HS-CH 2-CN.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Photochemistry of XCH₂CN (X = −Cl, −SH) in Argon Matrices

et al. 2019

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“…29 The five most stable isomers that were found using the procedure just described were subjected to more precise ab initio calculations to obtain more accurate energies. The final energy value was calculated in a fashion inspired by the HEAT 30 procedure in Cfour and described in our previous reports, 9,31 using the equation…”

Section: ■ Methodsmentioning

confidence: 99%

Structure and Spectroscopy of C₂HNO Isomers

2017

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Formyl cyanide has been detected toward Sgr B2 making this chemical and its potential isomers of astrophysical interest. We calculated the precise energies of the five most stable structural isomers of formyl cyanide and found that formyl isocyanide and 2H-azirin-2-one are less stable than formyl cyanide by 55 and 125 kJ/mol, respectively. We present our ab initio coupled cluster predictions of the spectroscopic parameters relevant to their gas-phase rotational and vibrational spectroscopy. Parameters include ground vibrational state rotational constants, centrifugal distortion parameters, equilibrium electric dipole moments, and nuclear quadrupole coupling constants. Anharmonic vibrational frequencies together with infrared intensities of fundamental and nonfundamental modes were also calculated. The broader potential energy surface, including transition states and the minima they connect, were explored for these isomers at the B3LYP/aug-cc-pVTZ level of theory. Formyl cyanide can dissociate in an exothermic reaction to form HCN and CO or in an endothermic reaction to form HNC and CO. The activation energies for both processes are close to 260 kJ/mol. The activation barrier for conversion of formyl cyanide into formyl isocyanide is ∼180 kJ/mol. The energetic barrier for the exothermic decomposition of formyl isocyanide into HNC and CO is ∼210 kJ/mol. The barrier for transformation of formyl isocyanide into formyl cyanide is ∼130 kJ/mol. Formyl isocyanide seems to be a stable chemical and could potentially survive in a dense molecular cloud if formed. These data are useful for future identification of members of this family of molecules in a laboratory or in space.

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Neptunium(V) Isothiocyanate Complexes with 4′-Aryl-Substituted 2,2′:6′,2″-Terpyridines and N,N-Dimethylacetamide as Molecular Ligands

et al. 2021

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New complexes of neptunyl(V) isothiocyanate with 4′-aryl-substituted 2,2′:6′,2″-terpyridines (Terpy) and N,N-dimethylacetamide (DMA) were obtained: [(NpO2)(4′-Ph-Terpy)(DMA)(NCS)]·DMA, [(NpO2)(4′-(4-(CF3)C6H4)-Terpy)(DMA)(NCS)]·2H2O·DMA, [(NpO2)(4′-(3-BrC6H4)-Terpy)(DMA)(NCS)]·DMA, and [(NpO2)(4′-(2-(COOH)C6H4)-Terpy)(DMA)(NCS)]·DMA. The structures of the compounds were determined with X-ray diffraction analysis. The neptunium coordination polyhedra were found to be pentagonal bipyramids with O atoms of the NpO2 groups in the apical positions and the equatorial planes formed by three N atoms of the terpyridine ligand, a N atom of the isothiocyanate anion, and an O atom of DMA. The influence of the substituents of the Ar group on the crystal structure is discussed. The IR spectra contain well-resolved bands of characteristic vibrations of all groups in the complex. The electronic absorption spectra are typical for neptunium(V) complexes and contain an intense narrow absorption band belonging to an f–f transition with a maximum of 988 nm and several long-wave satellites of lower intensity. The substituted terpyridines were shown to be efficient for the extraction of various valence forms of neptunium from the isothiocyanate solutions.

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A theoretical study on the spectroscopy, structure, and stability of C2H3NS molecules

Cited by 5 publications

References 70 publications

Photochemistry of XCH₂CN (X = −Cl, −SH) in Argon Matrices

Photochemistry of XCH₂CN (X = −Cl, −SH) in Argon Matrices

Structure and Spectroscopy of C₂HNO Isomers

Neptunium(V) Isothiocyanate Complexes with 4′-Aryl-Substituted 2,2′:6′,2″-Terpyridines and N,N-Dimethylacetamide as Molecular Ligands

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A theoretical study on the spectroscopy, structure, and stability of C2H3NS molecules

Cited by 5 publications

References 70 publications

Photochemistry of XCH2CN (X = −Cl, −SH) in Argon Matrices

Photochemistry of XCH2CN (X = −Cl, −SH) in Argon Matrices

Structure and Spectroscopy of C2HNO Isomers

Neptunium(V) Isothiocyanate Complexes with 4′-Aryl-Substituted 2,2′:6′,2″-Terpyridines and N,N-Dimethylacetamide as Molecular Ligands

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Product

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Photochemistry of XCH₂CN (X = −Cl, −SH) in Argon Matrices

Photochemistry of XCH₂CN (X = −Cl, −SH) in Argon Matrices

Structure and Spectroscopy of C₂HNO Isomers