The photoelectron spectra of perfluoro-2-butyne and perfluorohexa-2,4-diyne. The perfluorination effect

Delwiche, J.; Praet, M.-Th.; Caprace, G.; Hubin‐Franskin, M.‐J.; Natalis, P.; Collin, J.E.

doi:10.1016/0368-2048(77)85090-1

Cited by 10 publications

(7 citation statements)

References 18 publications

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“…In Table we show the calculated vertical IEs. As far as the second calculated IE is concerned, we note that the value is slightly higher than the obtained in the experimental work of Delwiche et al …”

Section: Resultscontrasting

confidence: 65%

“…Due to the proximity of this feature with the lowest ionic state at 12.76 eV, it is also tentatively assigned to the first member of the π(6e u ) → 3dσ series, with a quantum defect δ = −0.04. However, the lowest ionic band in 2-C 4 F 6 shows considerable extended vibrational excitation, 24 which we would expect to see in such Rydberg state. As reported in section C.1 for 1,3-C 4 F 6 , the lack of vibrational features can be attributed to the rather broad nature of the EEL features.…”

Section: Resultsmentioning

confidence: 79%

“…The lowest adiabatic ionization energy has been experimentally obtained from Delwiche et al's 24 He I photoelectron spectrum at 12.35 eV, and we have extracted a vertical value of 12.76 eV to be used in calculating the quantum defects associated with transitions to Rydberg orbitals (section C). Here, as in the previous C 4 F 6 isomers, the calculations show a mixing of valence and Rydberg states.…”

Section: Resultsmentioning

confidence: 99%

“…20 The infrared and Raman vibrational spectra of c-C 4 F 6 have been recorded by Klaeboe et al, 21 whereas Christophorou and co-workers present temperature dependence of electron attachment and detachment in c-C 4 F 6 . 22,23 As far as hexafluoro-2-butyne (2-C 4 F 6 ) is concerned, we report on the molecular structure work of Chang et al 11 and the (12.35 ± 0.01) eV adiabatic ionization energy of Delwiche et al 24 as provided by He I photoelectron spectra, with a detailed vibrational analysis of the first ionic band.…”

Section: Introductionmentioning

confidence: 98%

“…As far as hexafluoro-2-butyne (2-C 4 F 6 ) is concerned, we report on the molecular structure work of Chang et al and the (12.35 ± 0.01) eV adiabatic ionization energy of Delwiche et al as provided by He I photoelectron spectra, with a detailed vibrational analysis of the first ionic band.…”

Section: Introductionmentioning

confidence: 99%

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Electronic Excitation to Singlet States of 1,3-C₄F₆, c-C₄F₆ and 2-C₄F₆ by Electron Impact - Electron Energy-Loss Spectroscopy and ab Initio Calculations

et al. 2012

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We report on the first measurements of the electron impact electronic excitation cross sections for C(4)F(6) isomers, hexafluoro-1,3-butadiene (1,3-C(4)F(6)), hexafluorocyclobutene (c-C(4)F(6)), and hexafluoro-2-butyne (2-C(4)F(6)), measured at 100 eV, 3° scattering angle, while sweeping the energy loss over the range 2.0-15.0 eV. Under these experimental conditions, optically allowed transitions are favored. The electronic state spectroscopy has been investigated and the assignments supported by quantum chemical calculations. The n = 3 members of the Rydberg series have been assigned converging to the lowest ionization energy limits of the C(4)F(6) isomers and classified according to the magnitude of the quantum defects (δ).

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Section: Resultscontrasting

confidence: 65%

Section: Resultsmentioning

confidence: 79%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

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Electronic Excitation to Singlet States of 1,3-C₄F₆, c-C₄F₆ and 2-C₄F₆ by Electron Impact - Electron Energy-Loss Spectroscopy and ab Initio Calculations

et al. 2012

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Hartree—Fock—Slater-LCAO studies of the acetylene—transition metal interaction. III. Binding to mono- and dinuclear Ni complexes with carbonyl and isocyanide ligands

1981

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Fluorination effects on the inner-shell spectra of unsaturated molecules

Robin¹,

Ishii²,

McLaren³

et al. 1988

Journal of Electron Spectroscopy and Related Phenomena

133

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The applicability of the perfluoro effect to the X-ray spectra (300-800 eV) of unsaturated organic molecules is explored. The Cls and Fls (and 01s where appropriate) oscillator strength spectra of five fluoroethylenes, octafluorocyclopentene, formyl fluoride, carbonyl fluoride, hexafluorobutadiene, trifluoroacetic acid, heduorobutyne-2, hexafluoroacetone, and octatluoronaphthalene were derived from electron impact energy loss spectra recorded under electric-dipole scattering conditions. These spectra are analyzed and compared with those of their perhydro analogs, several of which (naphthalene, acetic acid, butyne-2) are reported for the first time. In unsaturated systems in which all the atoms lie in the molecular plane, such as ethylene, formaldehyde, benzene, etc., perfluorination results in approximately 10 eV shifts of the inner-shell energy loss spectra to higher energies, yet the term values for the Cls-, ln* excitations are shifted by only l eV and often less. In direct contrast, the term values for the equivalent C l s -+ l a * excitations in unsaturated systems having atoms out of the molecular plane, such as butene-2 and acetone, are shifted upward by up to 3 eV upon perfluorination. These different spectral behaviors of planar and nonplanar systems on fluorination quantitatively parallel those which were observed earlier for valence-level ionization potentials (10-20 eV) and attributed to the perfluoro effect. I t is observed for the first time that the Cls+ln* excitation energies in planar hydrocarbons are only very weakly dependent on the spatial extent of the n-electron system. An explanation involving a localized Cls hole is proposed to rationalize this behavior.The perfluoro effect also predicts that excitations to a* MO's will become relatively low-lying in highly fluorinated planar systems. Such low-lying inner-shell excitations induced by fluorination are observed in the fluoroethylene series and in the fluorocarbonyls. When the negative-ion spectra of the fluoroethylenes are assigned in a self-consistent manner, a a* MO is found to drop into the vicinity of In* upon fluorination. A similar intrusion of the lowest dr MO among the n+ MO's is also observed upon fluorinating benzene, while evidence for this in the case of naphthalene is less clear, on account of the complex pattern of multiple Cls-+nn* transitions in this molecule.

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The photoelectron spectra of perfluoro-2-butyne and perfluorohexa-2,4-diyne. The perfluorination effect

Cited by 10 publications

References 18 publications

Electronic Excitation to Singlet States of 1,3-C₄F₆, c-C₄F₆ and 2-C₄F₆ by Electron Impact - Electron Energy-Loss Spectroscopy and ab Initio Calculations

Electronic Excitation to Singlet States of 1,3-C₄F₆, c-C₄F₆ and 2-C₄F₆ by Electron Impact - Electron Energy-Loss Spectroscopy and ab Initio Calculations

Hartree—Fock—Slater-LCAO studies of the acetylene—transition metal interaction. III. Binding to mono- and dinuclear Ni complexes with carbonyl and isocyanide ligands

Fluorination effects on the inner-shell spectra of unsaturated molecules

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The photoelectron spectra of perfluoro-2-butyne and perfluorohexa-2,4-diyne. The perfluorination effect

Cited by 10 publications

References 18 publications

Electronic Excitation to Singlet States of 1,3-C4F6, c-C4F6 and 2-C4F6 by Electron Impact - Electron Energy-Loss Spectroscopy and ab Initio Calculations

Electronic Excitation to Singlet States of 1,3-C4F6, c-C4F6 and 2-C4F6 by Electron Impact - Electron Energy-Loss Spectroscopy and ab Initio Calculations

Hartree—Fock—Slater-LCAO studies of the acetylene—transition metal interaction. III. Binding to mono- and dinuclear Ni complexes with carbonyl and isocyanide ligands

Fluorination effects on the inner-shell spectra of unsaturated molecules

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Electronic Excitation to Singlet States of 1,3-C₄F₆, c-C₄F₆ and 2-C₄F₆ by Electron Impact - Electron Energy-Loss Spectroscopy and ab Initio Calculations

Electronic Excitation to Singlet States of 1,3-C₄F₆, c-C₄F₆ and 2-C₄F₆ by Electron Impact - Electron Energy-Loss Spectroscopy and ab Initio Calculations