Electron attachment and detachment: C6F6

Miller, Thomas M.; Doren, Jane M. Van; Viggiano, Albert A.

doi:10.1016/j.ijms.2003.11.014

Cited by 27 publications

(21 citation statements)

References 46 publications

(52 reference statements)

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“…We quote this here as a maximum value because the fit suggests that the 0-0 transition is not probed directly in the experiment. The measured ADE is in agreement with previous computational work [4][5][6] and our own electronic structure calculations which predict ADE = 0.55 eV.…”

Section: Computational Detailssupporting

confidence: 92%

“…Hexafluorobenzene, C6F6, has been extensively studied in electron attachment experiments as a text-book case in which the additional electron captured in the valence orbital of the anion leads to a dramatic Jahn-Teller distortion of the planar D6h geometry associated with the neutral [1][2][3][4][5][6][7] . More recently, it has been theoretically suggested that the C6F6 anion, C6F6 − , also possesses a non-valence state for which the electron binding is predominantly driven by correlation forces .…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Photoelectron Spectroscopy of the Hexafluorobenzene Cluster Anions: (C₆F₆)_n^– (n = 1–5) and I^–(C₆F₆)

et al. 2019

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Frequency-resolved (2D) photoelectron (PE) spectra of the anionic clusters (C6F6)n − , for n = 1-5, and time-resolved PE spectra of I − C6F6 are presented using a newly built instrument and supported by electronic structure calculations. From the 2D PE spectra, the vertical detachment energy (VDE) of C6F6 − was measured to be 1.60 ± 0.01 eV and the adiabatic detachment energy (ADE) ≤ 0.70 eV. The PE spectra also contain fingerprints of resonance dynamics over certain photon energy ranges, in agreement with the calculations. An action spectrum over the lowest resonance is also presented. The 2D spectra of (C6F6)n − show that the cluster can be described as C6F6 − (C6F6)n−1. The VDE increases linearly (200 ± 20 meV n −1) due to the stabilising influence on the anion of the solvating C6F6 molecules. For I − C6F6, action spectra of the absorption just below both detachment channels are presented. Timeresolved PE spectra of I − C6F6 excited at 3.10 eV and probed at 1.55 eV reveal a short-lived non-valence state of C6F6 − that coherently evolves into the valence ground state of the anion and induces vibrational motion along a specific buckling coordinate. Electronic structure calculations along the displacement of this mode show that at the extreme buckling angle, the probe can access an excited state of the anion that is bound at that geometry, but adiabatically unbound. Hence, slow electrons are emitted and show dynamics that probe predominantly the outer-turning point of the motion. A PE spectrum taken at t = 0 contains vibrational structure, assigned to a specific Raman and/or IR active mode of C6F6.

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Section: Computational Detailssupporting

confidence: 92%

Section: Introductionmentioning

confidence: 99%

Photoelectron Spectroscopy of the Hexafluorobenzene Cluster Anions: (C₆F₆)_n^– (n = 1–5) and I^–(C₆F₆)

et al. 2019

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“…24 This change is associated with a steep increase in the electron binding energy. At the minimum energy geometry of C6F6 -, the vertical and adiabatic binding energy are 1.45 and ~0.5 eV, respectively, [39][40][41] excluding the additional binding that arises from the cohesion energy of C6F6to I. Hence, for a probe photon with hv = 1.55 eV, we anticipate a reduced photoelectron yield at the minimum buckled geometry of I•C6F6 -.…”

Section: Discussionmentioning

confidence: 85%

Ultrafast dynamics of low-energy electron attachment via a non-valence correlation-bound state

2018

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The primary electron-attachment process in electron-driven chemistry represents one of the most fundamental chemical transformations with wide-ranging importance in science and technology. However, the mechanistic detail of the seemingly simple reaction of an electron and a neutral molecule to form an anion remains poorly understood, particularly at very low electron energies. Here, time-resolved photoelectron imaging was used to probe the electron-attachment process to a non-polar molecule using time-resolved methods. An initially populated diffuse non-valence state of the anion that is bound by correlation forces evolves coherently in ∼30 fs into a valence state of the anion. The extreme efficiency with which the correlation-bound state serves as a doorway state for low-energy electron attachment explains a number of electron-driven processes, such as anion formation in the interstellar medium and electron attachment to fullerenes.

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“…Using a flowing afterglow apparatus, Miller et al determined its EA a value to be 0.53 eV and also calculated it to be 0.45 eV. 21 Two purely theoretical studies have also been published. Xie et al 22 reported an EA a for C 6 F 6 of 0.69 eV, while Hou and Huang 23 reported its value to be 0.72-0.76 eV.…”

Section: Resultsmentioning

confidence: 99%

Photoelectron spectroscopy of hydrated hexafluorobenzene anions

Eustis

Wang

Bowen

et al. 2007

The Journal of Chemical Physics

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We present a synergetic experimental/theoretical study of hydrated hexafluorobenzene anions. Experimentally, we measured the anion photoelectron spectra of the anions, C6F6(-)(H2O)n (n=0-2). The spectra show broad peaks, which shift to successively higher electron binding energies with the addition of each water molecule to the hexafluorobenzene anion. Complementing these results, we also conducted density functional calculations which link adiabatic electron affinities to the optimized geometric structures of the negatively charged species and their neutral counterparts. Neutral hexafluorobenzene-water complexes are not thought to be hydrogen bonded. In the case of C6F6(-)(H2O)1, however, its water molecule was found to lie in the plane of the hexafluorobenzene anion, bound by two O-H...F ionic hydrogen bonds. Whereas in the case of C6F6(-)(H2O)2, both water molecules also lie in the plane of and are hydrogen bonded to the hexafluorobenzene anion but on opposite ends. This study and that of Schneider et al. [J. Chem. Phys. 127, 114311 (2007), preceding paper] are in agreement regarding the geometry of C6F6(-)(H2O)1.

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Electron attachment and detachment: C6F6

Cited by 27 publications

References 46 publications

Photoelectron Spectroscopy of the Hexafluorobenzene Cluster Anions: (C₆F₆)_n^– (n = 1–5) and I^–(C₆F₆)

Photoelectron Spectroscopy of the Hexafluorobenzene Cluster Anions: (C₆F₆)_n^– (n = 1–5) and I^–(C₆F₆)

Ultrafast dynamics of low-energy electron attachment via a non-valence correlation-bound state

Photoelectron spectroscopy of hydrated hexafluorobenzene anions

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Electron attachment and detachment: C6F6

Cited by 27 publications

References 46 publications

Photoelectron Spectroscopy of the Hexafluorobenzene Cluster Anions: (C6F6)n– (n = 1–5) and I–(C6F6)

Photoelectron Spectroscopy of the Hexafluorobenzene Cluster Anions: (C6F6)n– (n = 1–5) and I–(C6F6)

Ultrafast dynamics of low-energy electron attachment via a non-valence correlation-bound state

Photoelectron spectroscopy of hydrated hexafluorobenzene anions

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Product

Resources

About

Photoelectron Spectroscopy of the Hexafluorobenzene Cluster Anions: (C₆F₆)_n^– (n = 1–5) and I^–(C₆F₆)

Photoelectron Spectroscopy of the Hexafluorobenzene Cluster Anions: (C₆F₆)_n^– (n = 1–5) and I^–(C₆F₆)