The electronic states of 2-furanmethanol (furfuryl alcohol) studied by photon absorption and electron impact spectroscopies

Giuliani, Alexandre; Walker, Isobel C.; Delwiche, J.; Hoffmann, Søren Vrønning; Limão‐Vieira, P.; Mason, Nigel J.; Heyne, Belinda; Hoebeke, Maryse; Hubin‐Franskin, M.‐J.

doi:10.1063/1.1603733

Cited by 9 publications

(13 citation statements)

References 29 publications

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“…This experimentally found wavelength must correspond to the origin of transition to the first excited singlet state of FFA. This value is in a good agreement with the experimentally observed peak maxima of the UV-spectrum of FFA in the gas phase ( E max = 211 nm) and in solution ( E max = 218 nm) …”

Section: Resultssupporting

confidence: 90%

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Conformers, Infrared Spectrum and UV-Induced Photochemistry of Matrix-Isolated Furfuryl Alcohol

et al. 2012

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The infrared spectra of furfuryl alcohol (2-furanmethanol, FFA) were investigated for FFA monomers isolated in low-temperature argon matrices. The structural interpretation of the obtained experimental spectra was assisted by analysis of the molecule's conformational landscape. According to the DFT(B3LYP)/6-311++G(d,p) calculations, five different minimum energy structures were found on the potential energy surface of the molecule. They can be defined by the orientation of the OCCO and CCOH dihedral angles: GG', GG, TG, TT, GT (G = +gauche, G' = -gauche, T = trans) and have a symmetry equivalent configuration: GG' = G'G, GG = G'G', TG = TG', GT = G'T. When zero-point energies are taken into account, only three (GG', GG, and TT) out of the five unique minima correspond to stable structures. The most stable conformer GG' (OCCO, 72.7°; CCOH, -59.3°), which in gas phase at room temperature accounts for ∼65% of the total population, was the only form isolated in the argon matrices at 14 K. The other two relevant forms convert into conformer GG' during matrix deposition. The low temperature glassy and crystalline states of FFA were also obtained and their infrared spectra assigned, suggesting the sole existence of the GG' conformer also in these phases. The photochemical behavior of FFA induced in situ, by tunable UV-laser, was also studied. The longest wavelength resulting in photochemical changes in the structure of the irradiated sample was found to be λ = 229 nm. Such UV irradiation of the matrix-isolated FFA led to production of formaldehyde and different isomeric C(4)H(4)O species. Cycloprop-2-ene-1-carbaldehyde and buta-2,3-dienal (two conformers) are the main initial C(4)H(4)O photoproducts formed upon short-time excitation at λ = 229 nm. But-3-ynal (two conformers) was the principal photoproduct resulting from prolonged excitation at λ= 229 nm, being consumed upon irradiation at shorter wavelengths (λ < 227.5 nm). Vinyl ketene is produced from FFA in the trans conformation and undergoes isomerization to the cis form upon irradiation at λ < 227.5 nm. Cyclopropene, propyne, allene, and CO were also identified in the irradiated matrices (in particular at the later stages of irradiation), suggesting that the photoproduced aldehydes partially decarbonylate during the performed photochemical experiments.

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Section: Resultssupporting

confidence: 90%

“…Hence, all irradiations performed in the present study took place near the first absorption maximum of the compound. According to the literature, this band comprehends the transitions to the two first singlet states, with dominant contribution from the lowest energy transition. Both excited states were proposed to be of π* character .…”

Section: Resultsmentioning

confidence: 99%

Conformers, Infrared Spectrum and UV-Induced Photochemistry of Matrix-Isolated Furfuryl Alcohol

et al. 2012

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“…In forthcoming papers, the validity of this classification will be checked for other substituants, like CH 2 OH. 48 …”

Section: Discussionmentioning

confidence: 99%

2-methyl furan: An experimental study of the excited electronic levels by electron energy loss spectroscopy, vacuum ultraviolet photoabsorption, and photoelectron spectroscopy

Giuliani

Delwiche

Hoffmann³

et al. 2003

The Journal of Chemical Physics

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Articles you may be interested inValence and ionic lowest-lying electronic states of ethyl formate as studied by high-resolution vacuum ultraviolet photoabsorption, He(I) photoelectron spectroscopy, and ab initio calculationsThe electronic states of 1,2,3-triazole studied by vacuum ultraviolet photoabsorption and ultraviolet photoelectron spectroscopy, and a comparison with ab initio configuration interaction methods J. Chem. Phys. 134, 084309 (2011); 10.1063/1.3549812Electronic excitation spectrum of thiophene studied by symmetry-adapted cluster configuration interaction method Electronic excitation and oscillator strength of ethyl bromide by vacuum ultraviolet photoabsorption and electron energy loss spectroscopy Electronic excitation and oscillator strength of ethyl iodide by VUV photoabsorption and electron energy loss spectroscopyThe vacuum ultraviolet absorption spectrum of 2-methyl furan has been recorded between 5 eV ͑248 nm͒ and 9.91 eV ͑125 nm͒ and absolute photoabsorption cross sections measured. The electronic excited states of the molecule have also been probed using high resolution electron energy loss spectroscopy. Recorded under electric-dipole conditions, it has confirmed the magnitude of the photoabsorption cross section values and extended the optical oscillator strength values up to 12 eV. Measurements at several scattering angles have allowed the angular behavior of differential cross section ratios for some features in the 5-7.1 eV region to be measured, which in turn have helped in the assignments of electronic states to observed absorption bands. A high-resolution photoelectron spectrum was measured and allowed the two lowest ionization energies to be determined, these have been used in the identification of the related Rydberg states. Vibrational fine structure in the photoelectron spectrum has also been analyzed. The spectrum is dominated by intense -* transitions. Rydberg series associated with the first and second ionization energies have been identified. The effects of symmetry reduction induced on the furan ring by the methyl substitution are also discussed.

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“…Because of the considerable fragility of the sugar moiety against the nucleobases upon electron impact/transfer or photon absorption, several contributions have been reported (see, e.g., refs − and references therein). Tetrahydrofurfuryl alcohol (tetrahydro-2-furanmethanol) (THFA) has been recently studied by electron scattering − and electron impact ionization , methods and can be regarded as a transient structural form between tetrahydrofuran (THF) and deoxyribose, both of which have been investigated by photon, electron, positron, and neutral potassium impact. − We also note other structurally related ether and azole molecules that have been investigated in the context of the furan molecule. − …”

Section: Introductionmentioning

confidence: 99%

Electronic States of Tetrahydrofurfuryl Alcohol (THFA) As Studied by VUV Spectroscopy and Ab Initio Calculations

et al. 2014

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The electronic spectroscopy of isolated tetrahydrofuran (THF) in the gas phase has been investigated using high-resolution photoabsorption spectroscopy in the 5.8-10.6 eV with absolute cross section measurements derived. In addition, an electron energy loss spectrum was recorded at 100 eV and 10° over the 5-11.4 eV range. The He(I) photoelectron spectrum was also collected to quantify ionisation energies in the 9-16.1 eV spectral region. These experiments are supported by the first high-level ab initio calculations performed on the excited states of the neutral molecule and on the ground state of the positive ion. The excellent agreement between the theoretical results and the measurements allows us to solve several discrepancies concerning the electronic state spectroscopy of THF. The present work reconsiders the question of the lowest energy conformers of the molecule and its population distribution at room temperature.

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The electronic states of 2-furanmethanol (furfuryl alcohol) studied by photon absorption and electron impact spectroscopies

Cited by 9 publications

References 29 publications

Conformers, Infrared Spectrum and UV-Induced Photochemistry of Matrix-Isolated Furfuryl Alcohol

Conformers, Infrared Spectrum and UV-Induced Photochemistry of Matrix-Isolated Furfuryl Alcohol

2-methyl furan: An experimental study of the excited electronic levels by electron energy loss spectroscopy, vacuum ultraviolet photoabsorption, and photoelectron spectroscopy

Electronic States of Tetrahydrofurfuryl Alcohol (THFA) As Studied by VUV Spectroscopy and Ab Initio Calculations

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