Triplet π → π* and π → π* transitions in glyoxal and biacetyl by low-energy electron-impact spectroscopy

Verhaart, G.J.; Brongersma, H.H.

doi:10.1016/0009-2614(80)80268-5

Cited by 19 publications

(11 citation statements)

References 18 publications

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“…This state was also reported by other theoretical calculations, 18 however, the estimated values range widely as 3.47, 18 3.96, 68 4.97, 19 and 4.36 eV. 36 In higher energy region, we obtained the Rydberg transition 1 1 B u ͑n + → 3p x ͒ at 7.83 eV which agrees with the observed state at 7.9 eV by Verhaart and Brongersma, 7 but, their assignment was different as → * transition. Robin 69 assigned a diffuse band at 7.75 eV in Walsh's 1,70 optical spectrum to n + → 3p Rydberg state.…”

Section: State/naturesupporting

confidence: 90%

“…19 The valence 1 1 B g state was calculated at 4.68 eV in the present calculation and was characterized as the excitation from the n O + orbital. This result is corroborated by some experimental works such as the electron-impact spectroscopy of Verhaart and Brongersma; 7 the experimental values were reported as 4.2, 7 4.46, 66 and 4.63 eV ͑Ref. 67͒ for this state.…”

Section: State/naturesupporting

confidence: 75%

“…The UV absorption spectra of glyoxal and acrolein were first reported by Walsh and co-workers. [1][2][3] Later on, electron impact excitation, 4 electron energy loss spectroscopy ͑EELS͒, [5][6][7] UV absorption spectra, [8][9][10] resonance Raman scattering spectroscopy 11 methods were applied to these molecules. However, in some cases, contradictory results were obtained; for example, in trans-butadiene, resonance Raman scattering study showed that 1 1 B u state is energetically higher than 2 1 A g state, whereas multiphoton ionization ͑MPI͒ or EELS experiments reported the reverse order.…”

Section: Introductionmentioning

confidence: 99%

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Singly and doubly excited states of butadiene, acrolein, and glyoxal: Geometries and electronic spectra

Saha

Ehara²,

Nakatsuji³

2006

The Journal of Chemical Physics

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Excited-state geometries and electronic spectra of butadiene, acrolein, and glyoxal have been investigated by the symmetry adapted cluster configuration interaction (SAC-CI) method in their s-trans conformation. Valence and Rydberg states below the ionization threshold have been precisely calculated with sufficiently flexible basis sets. Vertical and adiabatic excitation energies were well reproduced and the detailed assignments were given taking account of the second moments. The deviations of the vertical excitation energies from the experiment were less than 0.3 eV for all cases. The SAC-CI geometry optimization has been applied to some valence and Rydberg excited states of these molecules in the planar structure. The optimized ground- and excited-state geometries agree well with the available experimental values; deviations lie within 0.03 A and 0.7 degrees for the bond lengths and angles, respectively. The force acting on the nuclei caused by the excitations has been discussed in detail by calculating the SAC-CI electron density difference between the ground and excited states; the geometry relaxation was well interpreted with the electrostatic force theory. In Rydberg excitations, geometry changes were also noticed. Doubly excited states (so-called 2 (1)A(g) states) were investigated by the SAC-CI general-R method considering up to quadruple excitations. The characteristic geometrical changes and large energetic relaxations were predicted for these states.

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Section: State/naturesupporting

confidence: 90%

Section: State/naturesupporting

confidence: 75%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Singly and doubly excited states of butadiene, acrolein, and glyoxal: Geometries and electronic spectra

Saha

Ehara²,

Nakatsuji³

2006

The Journal of Chemical Physics

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“…Glyoxal has two electron‐withdrawing oxygen atoms and its B g resonance is more bound as observed at 1.9 eV compared with butadiene (2.8 eV). The present calculations gave Re( E ) = 2.57–2.67 eV by the corrected trajectory as seen in Table and Supporting Information Figure S5.…”

Section: Resultsmentioning

confidence: 99%

Projected CAP/SAC‐CI method with smooth Voronoi potential for calculating resonance states

2015

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The complex absorbing potential (CAP)/symmetry-adapted cluster-configuration interaction (SAC-CI) method has been combined with a smooth Voronoi potential, which was recently introduced in the extrapolation procedure, to locate π* resonance states of small- to medium-size molecules. Here, the projected CAP/SAC-CI method is combined with this potential and used to calculate the double-bond and heteroaromatic π* resonances of acetaldehyde, butadiene, glyoxal, pyridine, pyrazine, and furan. As observed in the pilot applications, the corrected η-trajectories provide a stable resonance energy and width or lifetime regardless of the size parameter (rcut ) of the smooth Voronoi potential. However, in general, the stabilization behavior of the trajectories is clearer for larger rcut values, which implies that the interaction of the CAP with the valence electrons is more advantageously addressed by a larger "cavity" size.

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“…Setting aside the perspicuous role of O 2 , glyoxal is a tracer for the reaction pathways of biogenic compounds in the troposphere , as well as being a precursor to secondary organic aerosol formation , and has inspired a wide range of spectroscopic and theoretical studies. − Methylglyoxal is formed from the oxidation of diverse organic compounds in the troposphere − and its atmospheric interactions with glyoxal are of further interest, , while biacetyl is a ring-cleavage product in the NO x oxidation of aromatics, , with implications for cloud chemistry . These methylated analogs of glyoxal have also been the subject of spectroscopic examination. − …”

Section: Introductionmentioning

confidence: 99%

Autodetachment over Broad Photon Energy Ranges in the Anion Photoelectron Spectra of [O₂–M]⁻ (M = Glyoxal, Methylglyoxal, or Biacetyl) Complex Anions

et al. 2021

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Complexes of anion−neutral pairs are prevalent in chemical and physical processes in the interstellar medium, the atmosphere, and biological systems, among others. However, bimolecular anionic species that cannot be described as simple ion−molecule complexes due to their competitive electron affinities have received less attention. In this study, the [O 2 −M] − (M = glyoxal, methylglyoxal, or biacetyl) anion photoelectron spectra obtained with several different photon energies are reported and interpreted in the context of ab initio calculations. The spectra do not resemble the photoelectron spectra of M − or O 2 − "solvated" by a neutral partner. Rather, all spectra are dominated by nearthreshold autodetachment from what are likely transient dipole bound states of the cis conformers of the complex anions. Very low Franck−Condon overlap between the neutral M•O 2 van der Waals clusters and the partial covalently bound complex anions results in low-intensity, broad direct detachment observed in the spectra. The [O 2 -glyoxal] − spectra measured with 2.88 and 3.495 eV photon energies additionally exhibit features at ∼0.5 eV electron kinetic energy, which is more difficult to explain, though there are numerous quasibound states of the anion that may be involved. Overall, these features point to the inadequacy of describing the complex anions as simple ion−molecule complexes.

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Triplet π → π* and π → π* transitions in glyoxal and biacetyl by low-energy electron-impact spectroscopy

Cited by 19 publications

References 18 publications

Singly and doubly excited states of butadiene, acrolein, and glyoxal: Geometries and electronic spectra

Singly and doubly excited states of butadiene, acrolein, and glyoxal: Geometries and electronic spectra

Projected CAP/SAC‐CI method with smooth Voronoi potential for calculating resonance states

Autodetachment over Broad Photon Energy Ranges in the Anion Photoelectron Spectra of [O₂–M]⁻ (M = Glyoxal, Methylglyoxal, or Biacetyl) Complex Anions

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Triplet π → π* and π → π* transitions in glyoxal and biacetyl by low-energy electron-impact spectroscopy

Cited by 19 publications

References 18 publications

Singly and doubly excited states of butadiene, acrolein, and glyoxal: Geometries and electronic spectra

Singly and doubly excited states of butadiene, acrolein, and glyoxal: Geometries and electronic spectra

Projected CAP/SAC‐CI method with smooth Voronoi potential for calculating resonance states

Autodetachment over Broad Photon Energy Ranges in the Anion Photoelectron Spectra of [O2–M]− (M = Glyoxal, Methylglyoxal, or Biacetyl) Complex Anions

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Autodetachment over Broad Photon Energy Ranges in the Anion Photoelectron Spectra of [O₂–M]⁻ (M = Glyoxal, Methylglyoxal, or Biacetyl) Complex Anions