Torsional frequencies in the far infrared—V. Torsions around the CC signle bond in some benzaldehydes, furfural, and related compounds

Miller, Foil A.; Fateley, William G.; Witkowski, R.E.

doi:10.1016/0584-8539(67)80016-3

Cited by 193 publications

(30 citation statements)

References 13 publications

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“…28 This value is in reasonable agreement with that of 250 ± 40 cm −1 (0.031 ± 0.005 eV) as reported by Zwarich and Rabinowitz, 21 and with the relative population weight between trans to cis of ∼3:1 determined by Miller et al 29 using the torsional frequencies in the far infrared spectrum. Vibrational analysis of the two conformers of furfural has been carried out on the basis of their IR and Raman spectra by Rogojerov et al, 30 whereas Gandini and coworkers 20,31 have reported on the photochemistry of furfural in the (π * ← n) and the lowest (π * ← π) absorption bands.…”

Section: Brief Summary Of the Structure And Properties Of Furfuralsupporting

confidence: 79%

“…The values obtained for this energy difference agree with previous calculations 51 and are in reasonable accord with the experimental values 21,28 and experimentally observed conformer populations. 29 The optimized geometries of both the trans and cis conformers obtained at the B3LYP/augcc-pVDZ level were therefore deemed suitable to use for further computations. With a view to performing extensive electron scattering calculations within a minimal orbital basis single configuration interaction (MOB-SCI) framework, excited state calculations were performed at the full-single configuration interaction (FSCI) level.…”

Section: Methodsmentioning

confidence: 99%

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Electronic excitation of furfural as probed by high-resolution vacuum ultraviolet spectroscopy, electron energy loss spectroscopy, and ab initio calculations

Silva

Lange

Limão-Vieira

et al. 2015

The Journal of Chemical Physics

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Articles you may be interested inElectronic excitation of carbonyl sulphide (COS) by high-resolution vacuum ultraviolet photoabsorption and electron-impact spectroscopy in the energy region from 4 to 11 eV J. Chem. Phys. 142, 064303 (2015); 10.1063/1.4907200Valence and ionic lowest-lying electronic states of ethyl formate as studied by high-resolution vacuum ultraviolet photoabsorption, He(I) photoelectron spectroscopy, and ab initio calculations J. Chem. Phys. 141, 104311 (2014) The electronic spectroscopy of isolated furfural (2-furaldehyde) in the gas phase has been investigated using high-resolution photoabsorption spectroscopy in the 3.5-10.8 eV energy-range, with absolute cross section measurements derived. Electron energy loss spectra are also measured over a range of kinematical conditions. Those energy loss spectra are used to derive differential cross sections and in turn generalised oscillator strengths. These experiments are supported by ab initio calculations in order to assign the excited states of the neutral molecule. The good agreement between the theoretical results and the measurements allows us to provide the first quantitative assignment of the electronic state spectroscopy of furfural over an extended energy range. C 2015 AIP Publishing LLC. [http://dx

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Section: Brief Summary Of the Structure And Properties Of Furfuralsupporting

confidence: 79%

Section: Methodsmentioning

confidence: 99%

Electronic excitation of furfural as probed by high-resolution vacuum ultraviolet spectroscopy, electron energy loss spectroscopy, and ab initio calculations

Silva

Lange

Limão-Vieira

et al. 2015

The Journal of Chemical Physics

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“…[10][11][12][13][14][15][16][17][18][19][20] 3FA and 2FA have been found to exist in the gas phase, nematic and isotropic solutions, and neat liquid state, as a mixture of two planar conformers differing by rotation of the aldehyde group around the exocyclic C-C bond (cis and trans with respect to the ring oxygen atom; see Scheme 1). [21][22][23][24][25][26][27][28] For 2FA, the trans conformer was found to be the lowest energy form, with gas phase reported values for ∆E (cis-trans) ranging from 3.10 to 8.79 kJ mol -1 , [18][19][20][21][22][23][24][25][26][27] which implies a minimum expected population of the conformational ground state of 2FA at room temperature (RT) of ca. 80%.…”

Section: Introductionmentioning

confidence: 99%

Photoisomerization and Photochemistry of Matrix-Isolated 3-Furaldehyde

2010

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3-Furaldehyde (3FA) was isolated in an argon matrix at 12 K and studied using FTIR spectroscopy and quantum chemistry. The molecule has two conformers, with trans and cis orientation of the OdCsCdC dihedral angle. At the B3LYP/6-311++G(d,p) level of theory, the trans form was computed to be ca. 4 kJ mol -1 more stable than the cis form. The relative stability of the two conformers was explained using the natural bond orbital (NBO) method. In fair agreement with their calculated relative energies and the high barrier of rotamerization (ca. 34 kJ mol -1 from trans to cis), the trans and cis conformers were trapped in an argon matrix from the compound room temperature gas phase in proportion ∼7:1. The experimentally observed vibrational signatures of the two forms are in a good agreement with the theoretically calculated spectra. Broad-band UV-irradiation (λ > 234 nm) of the matrix-isolated compound resulted in partial trans f cis isomerization, which ended at a photostationary state with the trans/cis ratio being ca. 1.85:1. This result was interpreted based on results of time-dependent DFT calculations. Irradiation at higher energies (λ > 200 nm) led to decarbonylation of the compound, yielding furan, cyclopropene-3-carbaldehyde, and two C 3 H 4 isomers: cyclopropene and propadiene.

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“…The experimental values of the closely related benzene derivatives, benzamide, benzaldehyde and benzophenone [28,29] were therefore taken. These values may be assumed to be a close approximation to those of the pyridinium compounds NAD ÷ (sNAD+), fPdAD ÷ and ac3pdAD +, respectively, as benzaldehyde has the same rotation barrier as pyridine-3-aldehyde, 4.7 and 4.6 kcal/mol, respectively [29]. The …”

Section: Procedures For Calculational Studiesmentioning

confidence: 99%

NAD+ and NAD+ analogues in horse liver alcohol dehydrogenase. Relationship between reactivity and conformation simulated with molecular mechanics

Beijer

Buck

Sluyterman

et al. 1990

Biochimica et Biophysica Acta (BBA) - Protein Structure and Mol

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Torsional frequencies in the far infrared—V. Torsions around the CC signle bond in some benzaldehydes, furfural, and related compounds

Cited by 193 publications

References 13 publications

Electronic excitation of furfural as probed by high-resolution vacuum ultraviolet spectroscopy, electron energy loss spectroscopy, and ab initio calculations

Electronic excitation of furfural as probed by high-resolution vacuum ultraviolet spectroscopy, electron energy loss spectroscopy, and ab initio calculations

Photoisomerization and Photochemistry of Matrix-Isolated 3-Furaldehyde

NAD+ and NAD+ analogues in horse liver alcohol dehydrogenase. Relationship between reactivity and conformation simulated with molecular mechanics

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