Subfemtosecond Control of Molecular Fragmentation by Hard X-Ray Photons

Travnikova, Oksana; Sisourat, Nicolas; Marchenko, T.; Goldsztejn, Gildas; Guillemin, R.; Journel, L.; Céolin, Denis; Ismail, Iyas; Lago, A. F.; Püttner, R.; Piancastelli, M. N.; Simon, M.

doi:10.1103/physrevlett.118.213001

Cited by 29 publications

(30 citation statements)

References 32 publications

(42 reference statements)

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“…the resolving power E/ΔE higher than 5000 (where E is the kinetic energy of electron and ΔE the instrumental resolution), are quite scarce. Up to now, the GALAXIES beamline at the SOLEIL synchrotron [2,3] has been the only facility for high-resolution HAXPES experiments on atomic and molecular science and has been achieving significant results on double-core-hole spectroscopy [4][5][6][7], recoil effects [8][9][10], ultrafast phenomena [11][12][13], post-collision interaction (PCI) [14,15], resonant Auger processes [16][17][18][19][20], and very recent studies on aqueous solution [21,22]. The experiments at the GALAXIES beamline, however, are limited to the excitation energy ranging between 2.3 and 12 keV, while experiments with much higher photon energy are quite scarce.…”

Section: Introductionmentioning

confidence: 99%

Hard x-ray photoelectron spectroscopy on heavy atoms and heavy-element containing molecules using synchrotron radiation up to 35 keV at SPring-8 undulator beamlines

et al. 2019

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We have recently initiated hard x-ray photoelectron spectroscopy experiments on heavy atoms and heavy-element containing molecules in gas phase by using synchrotron radiation up to 35 keV at SPring-8 undulator beamlines. We have successfully measured deep inner-shell photoelectron spectra, as well as L-MM and M-NN Auger electron spectra excited below and above the K-edge of heavy elements. Target specimens utilized for the preliminary experiments are Ar, Kr and Xe atoms, and also iodine in iodomethane (CH 3 I) and trifluoroiodomethane (CF 3 I) molecules, respectively. We show some selected results on the extracted core-hole lifetime broadenings for the iodine 1s core level of the CH 3 I molecule and also for the Xe 2s, 2p core levels, to compare with theoretical values. The L-MM Auger electron spectra of Kr recorded at 13 and 16.6 keV excitation energies are also shown as typical examples, and the spectrum measured above the K-edge, i.e. 14.327 keV, is analyzed based on theoretical calculations using the Hartree-Fock method. As a result, we give a tentative assignment for the double-core-hole hyper-satellite LL-LMM Auger transitions of the Kr atom.

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Section: Introductionmentioning

confidence: 99%

Hard x-ray photoelectron spectroscopy on heavy atoms and heavy-element containing molecules using synchrotron radiation up to 35 keV at SPring-8 undulator beamlines

et al. 2019

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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: 98%

“…The observed narrowing effect occurs in CH 3 I at times significantly exceeding the determined 0.6 fs lifetime of the DCH state, when the population of this state is considerably depleted due to the Auger decay. However, it may play a role in molecules with light atomic constituents such as hydrogen halides undergoing fast dissociation [14].…”

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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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“…More specifically, Marchenko et al 22 obtained the topology of the potential energy surface (PES) and the lifetime of the DCH states of CH 3 I, by performing complementary measurements of resonant inelastic X-ray scattering (RIXS) and resonant Auger spectroscopy (RAS). Furthermore, the highly repulsive nature of DCH states leading to ultrafast dissociation has been illustrated by Travnikova et al 23,24 Finally, as was demonstrated by Céolin et al, 25 resonant energy transfer (RET) in SF 6 , due to the fill of an initial S 1s −1 vacancy by a S 2p electron, can lead to the formation of S 2p −1 F 1s −1 ts-DCH continuum states.…”

Section: Introductionmentioning

confidence: 87%

Double-core-hole states in CH3CN: Pre-edge structures and chemical-shift contributions

Koulentianos

Carniato

Püttner

et al. 2018

The Journal of Chemical Physics

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Spectra reflecting the formation of single-site double-core-hole pre-edge states involving the N 1s and C 1s core levels of acetonitrile have been recorded by means of high-resolution single-channel photoelectron spectroscopy using hard X-ray excitation. The data are interpreted with the aid of ab initio quantum chemical calculations, which take into account the direct or conjugate nature of this type of electronic states. Furthermore, the photoelectron spectra of N 1s and C 1s singly core-ionized states have been measured. From these spectra, the chemical shift between the two C 1s −1 states is estimated. Finally, by utilizing C 1s single and double core-ionization potentials, initial and final state effects for the two inequivalent carbon atoms have been investigated.

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Subfemtosecond Control of Molecular Fragmentation by Hard X-Ray Photons

Cited by 29 publications

References 32 publications

Hard x-ray photoelectron spectroscopy on heavy atoms and heavy-element containing molecules using synchrotron radiation up to 35 keV at SPring-8 undulator beamlines

Hard x-ray photoelectron spectroscopy on heavy atoms and heavy-element containing molecules using synchrotron radiation up to 35 keV at SPring-8 undulator beamlines

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

Double-core-hole states in CH3CN: Pre-edge structures and chemical-shift contributions

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