Electron Dynamics in the Core-Excited<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mrow><mml:msub><mml:mrow><mml:mi>CS</mml:mi></mml:mrow><mml:mrow><mml:mn>2</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math>Molecule Revealed through Resonant Inelastic X-Ray Scattering Spectroscopy

Marchenko, T.; Carniato, S.; Journel, L.; Guillemin, R.; Kawerk, Elie; Žitnik, M.; Kavčič, M.; Bučar, K.; Bohinc, R.; Petrič, M.; Cruz, Vinícius Vaz da; Gel’mukhanov, Faris; Simon, M.

doi:10.1103/physrevx.5.031021

Cited by 19 publications

(12 citation statements)

References 51 publications

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“…27,28 Our study contributes to demonstrating how time-resolved photoelectron spectroscopy complements other x-ray based probes of molecular gas-phase dynamics using ion spectroscopy, [29][30][31][32] x-ray absorption spectroscopy, [33][34][35][36][37] and x-ray scattering, 38 and it relates to core-hole induced dynamical effects in steady-state x-ray spectroscopy. 30,31,[39][40][41][42] Our study extends the demonstrated capabilities of time-resolved photoelectron spectroscopy with optical probe pulses, 18,43 and it shows how x-ray photoelectron spectroscopy complements other x-ray methods for the investigation of molecular dynamics. [44][45][46][47][48][49][50]…”

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confidence: 58%

Time-resolved electron spectroscopy for chemical analysis of photodissociation: Photoelectron spectra of Fe(CO)5, Fe(CO)4, and Fe(CO)3

Leitner

Josefsson

Mazza

et al. 2018

The Journal of Chemical Physics

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The prototypical photoinduced dissociation of Fe(CO) in the gas phase is used to test time-resolved x-ray photoelectron spectroscopy for studying photochemical reactions. Upon one-photon excitation at 266 nm, Fe(CO) successively dissociates to Fe(CO) and Fe(CO) along a pathway where both fragments retain the singlet multiplicity of Fe(CO). The x-ray free-electron laser FLASH is used to probe the reaction intermediates Fe(CO) and Fe(CO) with time-resolved valence and core-level photoelectron spectroscopy, and experimental results are interpreted with ab initio quantum chemical calculations. Changes in the valence photoelectron spectra are shown to reflect changes in the valence-orbital interactions upon Fe-CO dissociation, thereby validating fundamental theoretical concepts in Fe-CO bonding. Chemical shifts of CO 3σ inner-valence and Fe 3p core-level binding energies are shown to correlate with changes in the coordination number of the Fe center. We interpret this with coordination-dependent charge localization and core-hole screening based on calculated changes in electron densities upon core-hole creation in the final ionic states. This extends the established capabilities of steady-state electron spectroscopy for chemical analysis to time-resolved investigations. It could also serve as a benchmark for how charge and spin density changes in molecular dissociation and excited-state dynamics are expressed in valence and core-level photoelectron spectroscopy.

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Section: Fig 1 (A)supporting

confidence: 58%

Time-resolved electron spectroscopy for chemical analysis of photodissociation: Photoelectron spectra of Fe(CO)5, Fe(CO)4, and Fe(CO)3

Leitner

Josefsson

Mazza

et al. 2018

The Journal of Chemical Physics

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“…61 Furthermore, rearrangement processes observed herein are the result of extremely fast (femtosecond or attosecond regime) chemical reactions. 62 The [CH n ] + /[S] + coincidences appear as well-dened and hydrogen-resolved islands, each one with two maximum regions, as shown in Fig. 3(a) The mechanisms depicted in eqn (6) and 7are also in agreement with the previous work by Butler, 58 which observed that the release of neutral S species competes with the direct H 3 CS-SCH 3 bond cleavage.…”

Section: Ion-ion Coincidences and Fragmentation Mechanismssupporting

confidence: 87%

Are disulfide bonds resilient to double ionization? Insights from coincidence spectroscopy and ab initio calculations

et al. 2020

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“…As the probability of radiative relaxation of core-excited atoms increases with atomic number, both RIXS and RAS become equally relevant in the hard x-ray regime [5][6][7][8][9][10][11][12][13][14]. However, the major difference between these techniques appears in the electronic final states reached upon relaxation.…”

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confidence: 99%

Potential Energy Surface Reconstruction and Lifetime Determination of Molecular Double-Core-Hole States in the Hard X-Ray Regime

et al. 2017

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A combination of resonant inelastic x-ray scattering and resonant Auger spectroscopy provides complementary information on the dynamic response of resonantly excited molecules. This is exemplified for CH3I, for which we reconstruct the potential energy surface of the dissociative I 3d −2 double-core-hole state and determine its lifetime. The proposed method holds a strong potential for monitoring the hard x-ray induced electron and nuclear dynamic response of core-excited molecules containing heavy elements, where ab initio calculations of potential energy surfaces and lifetimes remain challenging.Hard x-ray radiation, with photon energy above 1 keV, can excite deep core shells of heavy atoms (Cl 1s, S 1s, I 2p etc) and may cause breakage of the chemical bonds and drastic changes to the electronic structure. The interplay between the induced nuclear and electron dynamics determines the response of a core-excited molecule. In the case of resonant excitation to a dissociative molecular state, the time evolution of the relaxation process is determined by the potential energy surface (PES) and the lifetime of the excited state. The so called "core-hole clock" spectroscopy (CHCS) allows probing ultrafast dynamics, occurring in a resonantly core-excited molecule within the core-hole lifetime, through control over the photon energy [1][2][3][4].Resonant inelastic x-ray scattering (RIXS) and resonant Auger electron spectroscopy (RAS) are the two CHCS techniques relevant, respectively, to the measurements of x-ray photons or Auger electrons emitted in the course of relaxation of core-excited molecular states. As the probability of radiative relaxation of core-excited atoms increases with atomic number, both RIXS and RAS become equally relevant in the hard x-ray regime [5][6][7][8][9][10][11][12][13][14]. However, the major difference between these techniques appears in the electronic final states reached upon relaxation. In the case of RIXS, the molecule remains neutral with an electron in the excited orbital and a single hole, whereas in the case of resonant spectator Auger decay, the molecule becomes singly charged with an electron in the excited orbital and a double hole.Spectroscopy of double core-hole (DCH) states, created either with intense XFEL radiation through multiphoton absorption [15][16][17] or with high-energy photons provided by synchrotron radiation [18][19][20][21][22][23], has been a hot topic in the recent years. Understanding the nuclear dynamics of DCH states in molecules, formed in the course of cascade relaxations, is of particular interest in relation to the radiation-induced damage in organic tissue and coherent diffraction imaging [24,25].In this Letter, we demonstrate an original method to extract information on the electron and nuclear dynamic response of molecules in DCH states, created with hard x-ray radiation. In contrast to soft x-ray region, where nuclear dynamics occurs in a core-excited state, a short lifetime of a core-excited state in the hard x-ray regime allows a simple and, hence...

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Electron Dynamics in the Core-ExcitedCS2Molecule Revealed through Resonant Inelastic X-Ray Scattering Spectroscopy

Cited by 19 publications

References 51 publications

Time-resolved electron spectroscopy for chemical analysis of photodissociation: Photoelectron spectra of Fe(CO)5, Fe(CO)4, and Fe(CO)3

Time-resolved electron spectroscopy for chemical analysis of photodissociation: Photoelectron spectra of Fe(CO)5, Fe(CO)4, and Fe(CO)3

Are disulfide bonds resilient to double ionization? Insights from coincidence spectroscopy and ab initio calculations

Potential Energy Surface Reconstruction and Lifetime Determination of Molecular Double-Core-Hole States in the Hard X-Ray Regime

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