Ultrafast dynamics of temporary anions probed through the prism of photodetachment

Anstöter, Cate S.; Bull, James N.; Verlet, Jan R. R.

doi:10.1080/0144235x.2016.1203522

Cited by 57 publications

(76 citation statements)

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“…Geometric displacements along the vibrational mode attributed to coupling the ground state geometries of the anion and neutral C6F6 at 120 cm -1 were sampled using Avogadro The PE image indicates that the emission is very anisotropic, peaking along the polarisation axis. The 2D-PE spectrum in Figure 3 show that the peak at highest eKE increases by an amount equal to the increase in hv, indicating that this feature corresponds to a direct detachment process 17 . The maximum of this peak has an electron binding energy, eBE = hv -eKE, defined as the vertical detachment energy (VDE).…”

Section: Computational Detailsmentioning

confidence: 94%

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 Detailsmentioning

confidence: 94%

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

et al. 2019

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“…8 As the anion formation process is mediated by temporary excited states of the anion (resonances), there have been many studies aimed at characterising the spectroscopy and resonances of pBQand, moreover, to elucidate the photophysical processes involved in stable anion formation. 6,10,[12][13][14][15][16]25,34 Schiedt and Weinkauf measured the photodetachment cross section of the jet-cooled radical anion within the 2.0 -2.5 eV photon energy range and identified several resonances above threshold. 8 At photon energies resonant with resonances, the dominant detachment pathway was an indirect autodetachment channel (as opposed to the direct detachment pathway).…”

Section: Introductionmentioning

confidence: 99%

Photoelectron spectroscopy of para-benzoquinone cluster anions

Mensa-Bonsu

Wilson

Tozer

et al. 2019

The Journal of Chemical Physics

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The full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that: • a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.

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“…[14][15][16][17] The dynamics of such resonances can have striking effects on the measured photoelectron spectra, since ultrafast excited state nuclear motion can compete with autodetachment. 18,19 These effects can take the form of changing Franck-Condon factors, internal conversion dynamics, or dissociation dynamics leading to an anionic fragment from which an electron is subsequently photodetached. Several recent photoelectron studies on conjugated anions have shown that photoexcitation of resonances followed by ground electronic state recovery is a very efficient process.…”

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Charged Particle Imaging of the Deprotonated Octatrienoic Acid Anion: Evidence for a Photoinduced Cyclization Reaction

West

Bull

Verlet

2016

J. Phys. Chem. Lett.

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. (2016) 'Charged particle imaging of the deprotonated octatrienoic acid anion : evidence for a photoinduced cyclization reaction.', The journal of physical chemistry letters., 7 (22). pp. 4635-4640. Further information on publisher's website:https://doi.org/10.1021/acs.jpclett.6b02302Publisher's copyright statement:This document is the Accepted Manuscript version of a Published Work that appeared in nal form in The journal of physical chemistry letters, copyright c American Chemical Society after peer review and technical editing by the publisher. To access the nal edited and published work see https://doi.org/10.1021/acs.jpclett.6b02302Additional information: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-pro t purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. (Figure 1) was generated by electrospray ionisation, mass-selected and intersected with laser pulses (~5 ns duration) at 4.13 eV (300 nm) or 4.66 eV (266 nm) at the centre of a perpendicular velocity-map imaging (VMI) spectrometer. 23,24 The VMI spectrometer has been optimised to perform photoelectron spectroscopy by gating the imaging detector with ~100 ns gate pulse and reconstructing the raw image. 25 However, the same perpendicular VMI spectrometer can also be used to image other charged species, such as H -. Supporting ground electronic structure calculations were performed at the G4 5 level of theory and resonance energetics computed at multi-state XCMQDPT2 level of theory. 26,27 The photoelectron spectra of [C7H9-CO2] -taken at hv = 4.13 eV and 4.66 eV are shown in Figure 1(a) and (b), respectively. The photoelectron spectra are dominated by a peak at low electron kinetic energy, eKE, which is generally indicative of the indirect electron loss process of thermionic emission. 15,20,28,29 In addition to this low eKE peak, there are several minor features at higher eKE. In the hν = 4.13 eV spectrum, the low eKE peak has a shoulder that extends up to ~1.4 eV and a weak feature that peaks at eKE ~ 2.5 eV as indicated by the asterisk in Figure 1(a). The photoelectron spectrum at hν = 4.66 eV, shown in Figure 1(b), is broadly similar, although the shoulder to the dominating low eKE peak is larger than at hν = 4.13 eV and extends to eKE ~1.9 eV, which is consistent with a direct photodetachment process. The hν = 4.66 eV spectrum does not, however, show the clear peak around eKE ~ 2.5 eV (or at eKE ~ 3.0 eV taking into account the additional photon energy).In addition to the peak at eKE ~ 2.5 eV in the hν = 4.13 eV photoelectron spectrum, a discernible peak is present at eKE ~ 3.3 eV, as indicated by the arrow in Fig...

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Ultrafast dynamics of temporary anions probed through the prism of photodetachment

Cited by 57 publications

References 122 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)

Photoelectron spectroscopy of para-benzoquinone cluster anions

Charged Particle Imaging of the Deprotonated Octatrienoic Acid Anion: Evidence for a Photoinduced Cyclization Reaction

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Ultrafast dynamics of temporary anions probed through the prism of photodetachment

Cited by 57 publications

References 122 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)

Photoelectron spectroscopy of para-benzoquinone cluster anions

Charged Particle Imaging of the Deprotonated Octatrienoic Acid Anion: Evidence for a Photoinduced Cyclization Reaction

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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)