An experimental and theoretical study of the valence shell photoelectron spectrum of sulphur hexafluoride

Holland, D.M.P.; MacDonald, M A; Baltzer, P.; Karlsson, Leif; Lundqvist, Maria; Wannberg, B.; Niessen, W. von

doi:10.1016/0301-0104(94)00381-j

Cited by 57 publications

(73 citation statements)

References 66 publications

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“…Band I, whose maximum is observed at 21.7 eV, can be attributed to the satellite structure originating from the 4a orbital (with a HF energy of 24. exhibits maxima at 40.5 and 43.8 eV. As the 1a orbital corresponds essentially to the F 2s orbital, a photoelectron peak with a binding energy around 40 eV occurs in many fluorine containing molecules, for example, CF 4 [54], SF 6 [55] and SiF 4 [56]. However, the peak profile and the number of separate components contributing to the structure, varies from molecule to molecule.…”

Section: Resultsmentioning

confidence: 99%

An experimental and theoretical study of the valence shell photoelectron spectrum of bromochlorofluoromethane

Holland

Potts

Karlsson

et al. 2010

J. Phys. B: At. Mol. Opt. Phys.

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The complete valence shell photoelectron spectrum of bromochlorofluoromethane (CHFClBr), covering the binding energy range ∼10–50 eV, has been recorded using synchrotron radiation and the observed structure has been interpreted using ionization energies and relative spectral intensities computed using the third-order algebraic-diagrammatic-construction (ADC(3)) scheme for the one-particle Green's function and the outer valence Green's function (OVGF) method. The theoretical results demonstrate that the inner valence region of the photoelectron spectrum is dominated by satellite structure. Angle-resolved photoelectron spectra, recorded at selected excitation energies, have enabled the orbital assignments for the outer valence bands to be confirmed. The four outermost photoelectron bands, ascribed to the two pairs of orbitals associated with the nominally chlorine and bromine lone-pairs, exhibit characteristic angular distributions. The photon energy dependent variations in the relative photoelectron band intensities provide additional support for the orbital assignments.

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Section: Resultsmentioning

confidence: 99%

An experimental and theoretical study of the valence shell photoelectron spectrum of bromochlorofluoromethane

Holland

Potts

Karlsson

et al. 2010

J. Phys. B: At. Mol. Opt. Phys.

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“…Indeed, the utility of wide energy coverage for discerning the parentage of nominally forbidden transitions has been made in previous studies on the origin of satellite spectra in inner-valence photoionization by Karlsson, Holland, and co-workers. [15][16][17][18][19] A primary goal of this study is to provide sufficient energydependent information so that it will be possible to identify the underlying cause for the production of the v ϩ ϭ(0,1,0) level.…”

Section: ͑1͒mentioning

confidence: 99%

Excitation of the symmetry forbidden bending mode in molecular photoionization

Miller

Poliakoff

Miller

et al. 2001

The Journal of Chemical Physics

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We present results on the energy dependence of the vibrational branching ratio for the bending mode in CO 2 3 u Ϫ1 photoionization. Specifically, we determine the v ϩ ϭ(0,1,0)/v ϩ ϭ(0,0,0) intensity ratio by detecting dispersed fluorescence from the electronically excited photoions. The results exhibit large deviations over a very wide energy range, 18Ͻh exc Ͻ190 eV. Production of the v ϩ ϭ(0,1,0) level of the ion from the v 0 ϭ(0,0,0) ground state is forbidden by symmetry, and while observations of such features are well established in photoelectron spectroscopy, their appearance is normally ascribed to vibronic coupling in the ionic hole state. In this case, we find that such explanations fail to account for the energy dependence of the branching ratio. These deviations indicate that the continuum photoelectron participates in transferring oscillator strength to the nominally forbidden vibrational transition. A theoretical framework is developed for interpreting the experimental data, and Schwinger variational calculations are performed. These calculations demonstrate that the continuum electron is responsible for the observation of the excited bending mode as well as its energy dependence. This is an intrachannel effect that is best described as photoelectron-induced vibronic symmetry breaking. This appears to be a general phenomenon, and it may be useful in illuminating connections between bond angle and photoionization spectroscopies. The magnitude of these deviations display the utility of vibrationally resolved studies, and the extent over which these changes occur underscores the necessity of broad range studies to elucidate slowly varying characteristics in photoionization continua.

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“…7 This publication also reported results from a Gaussian 03 calculation 9 which supported the MO assignments made by Klyagina et al 8 Figure 1 summarises the combined findings of these investigations, and correlates the MOs for SF 5 Cl with those of SF 6 of O h symmetry. While the ordering of the valence MOs in for SF 6 is well established, 10 we note that the ordering and assignments given for SF 5 Cl are based on more limited evidence. The kinetics and ionic products of the reactions of a large number of small cations with SF 5 Cl have been studied in a selected ion flow tube.…”

Section: Introductionmentioning

confidence: 80%

“…Figure 1 : Valence molecular orbitals (indicated by solid lines with numeric values in eV) assigned to energy maxima observed in experimental photoelectron spectra for SF 6 and SF 5 Cl. 6,10 Orbitals in brackets are thought to lie close in energy, but have not been resolved in experimental spectra. …”

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confidence: 99%

Vacuum Ultraviolet Negative Photoion Spectroscopy of SF5Cl

Simpson

2011

Two Studies in Gas-Phase Ion Spectroscopy

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____________________________________________________________Using vacuum-UV radiation from a synchrotron, gas-phase negative ions are detected by mass spectrometry following photoexcitation of SF 5 Cl. Cl − signal is much weaker, despite the S−Cl bond being significantly weaker than the S−F bond.Appearance energies for F − and Cl − of 12.7 ± 0.2 and 10.6 ± 0.2 eV are determined. The spectra suggest that these ions form indirectly by crossing of Rydberg states of SF 5 Cl onto an ion-pair continuum.

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An experimental and theoretical study of the valence shell photoelectron spectrum of sulphur hexafluoride

Cited by 57 publications

References 66 publications

An experimental and theoretical study of the valence shell photoelectron spectrum of bromochlorofluoromethane

An experimental and theoretical study of the valence shell photoelectron spectrum of bromochlorofluoromethane

Excitation of the symmetry forbidden bending mode in molecular photoionization

Vacuum Ultraviolet Negative Photoion Spectroscopy of SF5Cl

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