Photoelectron dynamics of the valence shells of benzene as a function of photon energy

Carlson, Thomas A.; Gérard, Patrick; Krause, Manfred O.; Grimm, Frederick A.; Pullen, B. P.

doi:10.1063/1.452391

Cited by 61 publications

(28 citation statements)

References 25 publications

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“…Its spectrum is centered around a photon energy of ħω = 16.0 eV as displayed in Fig. 2a Also shown in this figure are partial photoionisation cross sections of benzene, as previously determined by angle-resolved photoelectron spectroscopy 27 . The lowest five cationic electronic states are prepared with significant population in our experiment.…”

Section: Resultsmentioning

confidence: 76%

Few-femtosecond passage of conical intersections in the benzene cation

Galbraith¹,

Scheit

Golubev

et al. 2017

Nat Commun

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Observing the crucial first few femtoseconds of photochemical reactions requires tools typically not available in the femtochemistry toolkit. Such dynamics are now within reach with the instruments provided by attosecond science. Here, we apply experimental and theoretical methods to assess the ultrafast nonadiabatic vibronic processes in a prototypical complex system—the excited benzene cation. We use few-femtosecond duration extreme ultraviolet and visible/near-infrared laser pulses to prepare and probe excited cationic states and observe two relaxation timescales of 11 ± 3 fs and 110 ± 20 fs. These are interpreted in terms of population transfer via two sequential conical intersections. The experimental results are quantitatively compared with state-of-the-art multi-configuration time-dependent Hartree calculations showing convincing agreement in the timescales. By characterising one of the fastest internal conversion processes studied to date, we enter an extreme regime of ultrafast molecular dynamics, paving the way to tracking and controlling purely electronic dynamics in complex molecules.

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Section: Resultsmentioning

confidence: 76%

Few-femtosecond passage of conical intersections in the benzene cation

Galbraith¹,

Scheit

Golubev

et al. 2017

Nat Commun

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“…8 × 10 -18 cm 2 molecule -1 . 36 Thus, the detection sensitivity of chlorobenzene derivatives in the VUV-SPI-TOFMS is expected to be higher than benzene derivatives (e.g. benzene, toluene, and xylene).…”

Section: I(cb)mentioning

confidence: 99%

Detection of Chlorobenzene Derivatives Using Vacuum Ultraviolet Ionization Time-of-Flight Mass Spectrometry

2003

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Vacuum ultraviolet single-photon ionization time-of-flight mass spectrometry (VUV-SPI-TOFMS) has been applied for the detection of chlorobenzene, o-dichlorobenzene, and o-chlorophenol as surrogates for polychlorinated dibenzo-pdioxine/furans (PCDD/F). The photoionization mass spectra of these compounds appear to be fragmentation free in the ionization processes by the VUV-SPI at 10.2 eV (121.6 nm). Quantum chemical calculations support no fragmentation in the photoionization of chlorobenzene derivatives at around 10 eV. The absolute photoionization cross-sections of chlorobenzene, o-dichlorobenzene, and o-chlorophenol were estimated at 10.2 eV. The photoionization cross-section is an important parameter in the detection of chlorobenzene derivatives by the single-photon ionization technique. The detection limit for chlorobenzene is on the order of tenth parts-per-billion volume (ppbv) in the present experimental setup.

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“…They embody the basic physics of such systems including the strong correlation effects in aromatic π-systems 84,89,92 and the self-interaction effects introduced by the nitrogen lone pairs. 51,59 Another advantage of these systems is that they are well-characterized experimentally [93][94][95][96][97][98][99][100][101][102][103][104][105][106][107][108] and well-studied theoretically by high-level wavefunction and Green's function methods. 93,104,[109][110][111][112][113][114][115][116][117][118][119][120][121][122] We calculate the electronic structure of benzene, pyridine, and the diazines using: (i) semi-local and hybrid DFT (ii) G 0 W 0 , (iii) ev-scGW, (iv) scGW 0 , (v) scGW, and (vi) G 0 W 0 combined with the second-order exchange self-energy (2OX), as an attempt to go beyond the GW approximation.…”

Section: Introductionmentioning

confidence: 99%

Benchmark ofGWmethods for azabenzenes

et al. 2012

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Many-body perturbation theory in the GW approximation is a useful method for describing electronic properties associated with charged excitations. A hierarchy of GW methods exists, starting from non-self-consistent G 0 W 0 , through partial self-consistency in the eigenvalues (evscGW) and in the Green's function (scGW 0 ), to fully self-consistent GW (scGW). Here, we assess the performance of these methods for benzene, pyridine, and the diazines. The quasiparticle spectra are compared to photoemission spectroscopy (PES) experiments with respect to all measured particle removal energies and the ordering of the frontier orbitals. We find that the accuracy of the calculated spectra does not match the expectations based on their level of selfconsistency. In particular, for certain starting points G 0 W 0 and scGW 0 provide spectra in better agreement with the PES than scGW.

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Photoelectron dynamics of the valence shells of benzene as a function of photon energy

Cited by 61 publications

References 25 publications

Few-femtosecond passage of conical intersections in the benzene cation

Few-femtosecond passage of conical intersections in the benzene cation

Detection of Chlorobenzene Derivatives Using Vacuum Ultraviolet Ionization Time-of-Flight Mass Spectrometry

Benchmark ofGWmethods for azabenzenes

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