A study of the electronic structure of the hexafluorobenzene and pentafluorobenzene molecules by ultrasoft X-ray emission spectroscopy

Davydova, N. V.; Yumatov, V. D.

doi:10.1134/s0036024410010073

Cited by 5 publications

(1 citation statement)

References 9 publications

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“…Fluorobenzene and the polyfluorobenzenes have been modeled more extensively than their pyridine counterparts, − most extensively by Jezowski, but with focus primarily on frontier orbitals rather than on the entire π-system and its effects on the structure and stability of the ring.…”

Section: Introductionmentioning

confidence: 99%

Fluoromaticity: The Molecular Orbital Contributions of Fluorine Substituents to the π-Systems of Aromatic Rings

2021

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The addition of fluorine atoms to an aromatic ring brings about an additional set of π-bonding and antibonding orbitals culminating after the addition of the sixth fluorine with a new set of π-aromatic-like orbitals that affect the molecule in a way that we will refer to hereafter as "fluoromaticity". Depending on the number and position of the fluorine atoms, the contributed πorbitals can even further stabilize the ring leading to smaller bond lengths within the ring and higher resistance to addition reactions. This added ring stability partially explains the high thermostability and chemical resistance found in polymers containing fluorinated aromatics in their architecture. A similar molecular orbital effect is seen with the addition of other halogen atoms to aromatic rings, though to a much smaller degree and not resulting in the additional ring stability.

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Section: Introductionmentioning

confidence: 99%

Fluoromaticity: The Molecular Orbital Contributions of Fluorine Substituents to the π-Systems of Aromatic Rings

2021

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Imaging large amplitude out-of-plane motion in photoexcited pentafluorobenzene using time-resolved photoelectron spectroscopy: a computational study

Sala

Egorova

2018

Photochem Photobiol Sci

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Excited-state dynamics of pentafluorobenzene is studied in detail for a quartic vibronic coupling model including the six b1 vibrational modes of the molecule and the two lowest excited electronic states. The study analyzes the influence of the large-amplitude out-of-plane vibrational motion on the electronic dynamics and extends to the simulation of the emerging time-resolved photoelectron spectra. The mapping of coherent non-separable electron-nuclear motion into oscillatory photoelectron signals is discussed.

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Long-lived coherence in pentafluorobenzene as a probe of ππ* – πσ* vibronic coupling

Hüter

Sala

Neumann

et al. 2016

The Journal of Chemical Physics

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The dynamics of pentafluorobenzene after femtosecond laser excitation to the optically bright ππ(*) first excited electronic state have been investigated by femtosecond time-resolved time-of-flight mass spectrometry and femtosecond time-resolved photoelectron imaging spectroscopy. The observed temporal profiles exhibit a bi-exponential decay behavior with a superimposed, long-lived, large-amplitude oscillation with a frequency of νosc = 78-74 cm(-1) and a damping time of τD = 5-2 ps. On the basis of electronic structure and quantum dynamics calculations, the oscillations have been shown to arise due to vibronic coupling between the optically bright ππ(*) state and the energetically close-lying optically dark πσ(*) state. The coupling leads to a pronounced double-well character of the lowest excited adiabatic potential energy surface along several out-of-plane modes of b1 symmetry. The optical electronic excitation initiates periodic wavepacket motion along these modes. In the out-of-plane distorted molecular configuration, the excited state acquires substantial πσ(*) character, thus modulating the ionization probability. The photoelectron spectra and the anisotropy of their angular distribution confirm the periodically changing electronic character. The ionizing probe laser pulse directly maps the coupled electron-nuclear motion into the observed signal oscillations.

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A study of the electronic structure of the hexafluorobenzene and pentafluorobenzene molecules by ultrasoft X-ray emission spectroscopy

Cited by 5 publications

References 9 publications

Fluoromaticity: The Molecular Orbital Contributions of Fluorine Substituents to the π-Systems of Aromatic Rings

Fluoromaticity: The Molecular Orbital Contributions of Fluorine Substituents to the π-Systems of Aromatic Rings

Imaging large amplitude out-of-plane motion in photoexcited pentafluorobenzene using time-resolved photoelectron spectroscopy: a computational study

Long-lived coherence in pentafluorobenzene as a probe of ππ* – πσ* vibronic coupling

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