The force field and molecular structure of dimethylsulfoxide from spectroscopic and gas electron diffraction data and ab initio calculations

Typke, V.; Dakkouri, Marwan

doi:10.1016/s0022-2860(01)00850-x

Cited by 23 publications

(27 citation statements)

References 43 publications

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“…The symmetry of its overall rotation was C s with symmetry number = 1. The molecular structure calculated using the B3LYP/6-311 + G(2df, p) is in good agreement with that determined experimentally [50] and is given in Table S1. The principal moments of inertia used for the calculation of the contributions of the general rotation were I A = 1.212 × 10 −45 kg m 2 , I B = 1.240 × 10 −45 kg m 2 , and I C = 2.029 × 10 −45 kg m 2 .…”

Section: T/ksupporting

confidence: 78%

Recommended vapor pressures for thiophene, sulfolane, and dimethyl sulfoxide

Fulem

Růžička

2011

Fluid Phase Equilibria

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Section: T/ksupporting

confidence: 78%

Recommended vapor pressures for thiophene, sulfolane, and dimethyl sulfoxide

Fulem

Růžička

2011

Fluid Phase Equilibria

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“…The bonding description of formally hypervalent molecules requires inclusion of both electron correlation and polarization functions [38]. The crucial importance of polarization functions, particularly of the f-type was also previously emphasized in studies of the relative energies of sulfur-containing molecules of the C 2 S 2 H 2 type [39,40].…”

Section: Geometry Of Mbidmentioning

confidence: 99%

Molecular structure and infrared spectra of the monomeric 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide (methyl pseudosaccharyl ether)

Kaczor

Almeida

Gómez‐Zavaglia

et al. 2008

Journal of Molecular Structure

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The computational description of saccharin (1,2-benzisothiazol-3(2H)-one-1,1-dioxide) and its derivatives is difficult due to the presence of hypervalent S@O bonds in their structures. Therefore, in this investigation, the HF, DFT/B3LYP and MP2 methods were used to predict the geometry and the infrared spectrum of the saccharyl derivative 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide (MBID). Their relative predictive capabilities were then evaluated by comparing the obtained results with experimentally available data, namely the newly obtained IR spectra of MBID isolated in low-temperature inert matrices. For each method, different basis sets [6-31++G(d,p), 6-31++G(3df,3pd), 6-311++G(d,p), 6-311++G(2df,2pd), 6-311++G(3df,3pd), aug-cc-pVDZ and aug-cc-pVTZ] were considered. The best overall agreement has been achieved at the B3LYP/6-311++G(3df,3pd) and B3LYP/6-31++G(3df,3pd) levels of theory, showing the adequacy of the B3LYP functional to describe the investigated properties in this type of compounds and stressing the relevance of including high-order polarization functions in the basis set.The chosen level of theory 3pd)] was applied to analyze the vibrational spectra and the geometry of the title molecule. In agreement with the experiment, the CAOAC linkage in MBID is predicted by these calculations to exhibit considerably short (1.320 Å ) and long (1.442 Å ) (N@)CAO and (H 3 )CAO bonds, respectively, and a hybridization of the central oxygen atom close to sp 2 (the CAOAC angle is predicted to be ca. 117°). This CAOAC bonding pattern fits the well-known high reactivity of MBID upon thermal rearrangement, which has been shown to result in easy selective [1,3 0 ]-isomerization of the compound.

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“…However, the intensities of the corresponding absorption bands were 1-2 orders of magnitude weaker than that of stretching vibration ν 3 .) Table 2 compares characteristics of the UCl 4 vibrational spectrum that were calculated in a harmonic approximation with experimental data for the gas phase at ~900 K [21]. The frequencies (in cm -1 ) and band intensities in the experimental spectra (in percent absorption) are also given.…”

mentioning

confidence: 99%

“…The molecular structure of DMSO has been studied several times by experimental and theoretical methods [21,[24][25][26][27]. The geometric parameters of DMSO were determined highly accurately.…”

mentioning

confidence: 99%

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Structure and vibrational IR spectra of a UCl4⋅2DMSO complex

et al. 2012

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UDC 539.19 Structural models are designed and spectral characteristics are computed based on DFT calculations for a complex of uranium tetrachloride with two molecules of dimethylsulfoxide (UCl 4 ⋅2DMSO). The calculations were carried out using a B3LYP hybrid functional in the LANL2DZ effective core potential approximation for the uranium atom and a cc-pVDZ all-electron basis set for all other atoms. Two structural variants were found for the complex. In the first of them, which is more stable, DMSO molecules are coordinated to the central uranium atom through oxygen atoms whereas in the second one, whose energy is 225 kJ/mol higher, the coordination proceeds through sulfur atoms. The obtained spectral characteristics are analyzed and compared with experimental data. Spectral features that are characteristic of the complexation process are identified. The adequacy of the proposed models and the agreement between calculation and experiment are demonstrated.Introduction. Dimethylsulfoxide (DMSO) occupies a special place among polar organic solvents containing C=O, S=O, or P=O electron-donating groups and; consequently, tending to form coordination complexes. In contrast with dimethylformamide (DMF), hexamethylphosphoramide (HMPA), and other compounds, DMSO can coordinate to the central metal atom in certain instances not only through the O atom but also through the S atom [1][2][3][4][5]. The latter type of coordination is accompanied by a short-wavelength shift of the S=O stretching vibrational frequency whereas coordination of the former type shifts the frequency to longer wavelength. Thus, the spectral position of this vibrational frequency can act as a highly reliable signature of the complex structure.Herein structural variants of the complex of UCl 4 with two DMSO molecules are discussed based on quantum-chemical calculations of the electronic structure and an analysis of previously obtained IR spectra [6,7]. Such complexes provide an example of polymerization involving organic and inorganic ligands and, in particular, can serve as a model for uranium complexation. Their spectral and structural characteristics can be used for the preparation of uranium oxides that are used in nuclear energy.Experimental and Calculations. IR absorption spectra of pure DMSO and UCl 4 ⋅2DMSO pressed into KBr pellets [6], suspended in a mineral-oil mull [7] for the middle IR region, or pressed into a polymeric matrix [6] for the long-wavelength region were recorded on a Vertex 70 spectrophotometer (Bruker) in the ranges 400-4000 cm

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The force field and molecular structure of dimethylsulfoxide from spectroscopic and gas electron diffraction data and ab initio calculations

Cited by 23 publications

References 43 publications

Recommended vapor pressures for thiophene, sulfolane, and dimethyl sulfoxide

Recommended vapor pressures for thiophene, sulfolane, and dimethyl sulfoxide

Molecular structure and infrared spectra of the monomeric 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide (methyl pseudosaccharyl ether)

Structure and vibrational IR spectra of a UCl4⋅2DMSO complex

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