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| 4. |
- Alonso-Mori, R., et al.
(författare)
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Towards characterization of photo-excited electron transfer and catalysis in natural and artificial systems using XFELs
- 2016
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Ingår i: Faraday discussions. - : Royal Society of Chemistry (RSC). - 1359-6640 .- 1364-5498. ; 194, s. 621-638
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Tidskriftsartikel (refereegranskat)abstract
- The ultra-bright femtosecond X-ray pulses provided by X-ray Free Electron Lasers (XFELs) open capabilities for studying the structure and dynamics of a wide variety of biological and inorganic systems beyond what is possible at synchrotron sources. Although the structure and chemistry at the catalytic sites have been studied intensively in both biological and inorganic systems, a full understanding of the atomic-scale chemistry requires new approaches beyond the steady state X-ray crystallography and X-ray spectroscopy at cryogenic temperatures. Following the dynamic changes in the geometric and electronic structure at ambient conditions, while overcoming X-ray damage to the redox active catalytic center, is key for deriving reaction mechanisms. Such studies become possible by using the intense and ultra-short femtosecond X-ray pulses from an XFEL, where sample is probed before it is damaged. We have developed methodology for simultaneously collecting X-ray diffraction data and X-ray emission spectra, using an energy dispersive spectrometer, at ambient conditions, and used this approach to study the room temperature structure and intermediate states of the photosynthetic water oxidizing metallo-protein, photosystem II. Moreover, we have also used this setup to simultaneously collect the X-ray emission spectra from multiple metals to follow the ultrafast dynamics of light-induced charge transfer between multiple metal sites. A Mn-Ti containing system was studied at an XFEL to demonstrate the efficacy and potential of this method.
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| 5. |
- Iablonskyi, D., et al.
(författare)
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Interatomic Coulombic Decay Processes after Multiple Valence Excitations in Ne Clusters
- 2015
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Ingår i: Journal of Physics: Conference Series. - : IOP Publishing. - 1742-6596 .- 1742-6588. ; 635, s. 112067-112067
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Konferensbidrag (refereegranskat)abstract
- We present a comprehensive analysis of autoionization processes in Ne clusters (similar to 5000 atoms) after multiple valence excitations by free electron laser radiation. The evolution from 2-body interatomic Coulombic decay (ICD) to 3-body ICD is demonstrated when changing from surface to bulk Frenkel exciton excitation. Super Coster-Kronig type 2-body ICD is observed at Wannier exciton which quenches the main ICD channel.
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| 6. |
- Iablonskyi, D., et al.
(författare)
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Slow Interatomic Coulombic Decay of Multiply Excited Neon Clusters
- 2016
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Ingår i: Physical Review Letters. - 0031-9007. ; 117:27
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Tidskriftsartikel (refereegranskat)abstract
- Ne clusters (∼5000 atoms) were resonantly excited (2p→3s) by intense free electron laser (FEL) radiation at FERMI. Such multiply excited clusters can decay nonradiatively via energy exchange between at least two neighboring excited atoms. Benefiting from the precise tunability and narrow bandwidth of seeded FEL radiation, specific sites of the Ne clusters were probed. We found that the relaxation of cluster surface atoms proceeds via a sequence of interatomic or intermolecular Coulombic decay (ICD) processes while ICD of bulk atoms is additionally affected by the surrounding excited medium via inelastic electron scattering. For both cases, cluster excitations relax to atomic states prior to ICD, showing that this kind of ICD is rather slow (picosecond range). Controlling the average number of excitations per cluster via the FEL intensity allows a coarse tuning of the ICD rate.
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| 8. |
- Takanashi, T, et al.
(författare)
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Time-Resolved Measurement of Interatomic Coulombic Decay Induced by Two-Photon Double Excitation of Ne2
- 2017
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Ingår i: Physical Review Letters. - 0031-9007. ; 118:3
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Tidskriftsartikel (refereegranskat)abstract
- The hitherto unexplored two-photon doubly excited states [Ne∗(2p-13s)]2 were experimentally identified using the seeded, fully coherent, intense extreme ultraviolet free-electron laser FERMI. These states undergo ultrafast interatomic Coulombic decay (ICD), which predominantly produces singly ionized dimers. In order to obtain the rate of ICD, the resulting yield of Ne2+ ions was recorded as a function of delay between the extreme ultraviolet pump and UV probe laser pulses. The extracted lifetimes of the long-lived doubly excited states, 390(-130/+450) fs, and of the short-lived ones, less than 150 fs, are in good agreement with ab initio quantum mechanical calculations.
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| 10. |
- Barillot, T., et al.
(författare)
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Correlation-Driven Transient Hole Dynamics Resolved in Space and Time in the Isopropanol Molecule
- 2021
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Ingår i: Physical Review X. - : American Physical Society. - 2160-3308. ; 11:3
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Tidskriftsartikel (refereegranskat)abstract
- The possibility of suddenly ionized molecules undergoing extremely fast electron hole (or hole) dynamics prior to significant structural change was first recognized more than 20 years ago and termed charge migration. The accurate probing of ultrafast electron hole dynamics requires measurements that have both sufficient temporal resolution and can detect the localization of a specific hole within the molecule. We report an investigation of the dynamics of inner valence hole states in isopropanol where we use an x-ray pump-x-ray probe experiment, with site and state-specific probing of a transient hole state localized near the oxygen atom in the molecule, together with an ab initio theoretical treatment. We record the signature of transient hole dynamics and make the first tentative observation of dynamics driven by frustrated Auger-Meitner transitions. We verify that the effective hole lifetime is consistent with our theoretical prediction. This state-specific measurement paves the way to widespread application for observations of transient hole dynamics localized in space and time in molecules and thus to charge transfer phenomena that are fundamental in chemical and material physics.
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| 12. |
- Kjellsson, Ludvig, et al.
(författare)
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Resonant Inelastic X-Ray Scattering Reveals Hidden Local Transitions of the Aqueous OH Radical
- 2020
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Ingår i: Physical Review Letters. - : AMER PHYSICAL SOC. - 0031-9007 .- 1079-7114. ; 124:23
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Tidskriftsartikel (refereegranskat)abstract
- Resonant inelastic x-ray scattering (RIXS) provides remarkable opportunities to interrogate ultra-fast dynamics in liquids. Here we use RIXS to study the fundamentally and practically important hydroxyl radical in liquid water, OH(aq). Impulsive ionization of pure liquid water produced a short-lived population of OH(aq), which was probed using femtosecond x-rays from an x-ray free-electron laser. We find that RIXS reveals localized electronic transitions that are masked in the ultraviolet absorption spectrum by strong charge-transfer transitions-thus providing a means to investigate the evolving electronic structure and reactivity of the hydroxyl radical in aqueous and heterogeneous environments. First-principles calculations provide interpretation of the main spectral features.
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| 13. |
- Kumagai, J, et al.
(författare)
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ESR, ENDOR, and ESEEM spectroscopy study on the local structure and motion of reactants : Highly selective tunneling radical abstraction in a neopentane-ethane mixture
- 2001
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Ingår i: Journal of Physical Chemistry A. - : American Chemical Society (ACS). - 1089-5639 .- 1520-5215. ; 105:14, s. 3652-3657
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Tidskriftsartikel (refereegranskat)abstract
- Local structures and motions of radical reactants in highly selective tunneling abstraction reaction in neopentane-ethane mixture are investigated with CW-ESR, ENDOR, and ESEEM spectroscopy at different temperatures. H atoms produced by the radiolysis of neo-C5H12 in the neo-C5H12-C2H6 (2 mol %) mixtures above 40 K react selectively with the solute C2H6 to give ethyl radicals. The selective reaction is suppressed below 30 K. The local structures of neopentane matrix around neopentyl and ethyl radicals are approximately the same in the temperature range from 4.4 to 45 K. Although neopentyl radicals are rigidly trapped below 100 K, ethyl radicals in neopentane matrix begin to librate even at 6 K and increase the degree of motion up to 30 K, Finally, the librating motion of the ethyl radicals in neopentane matrix is vigorous above 40 K. The ethane molecule can take more favorable orientation for the hydrogen abstraction reaction by H atoms than rigid neopentane molecules by the vigorous libration motion, resulting in the selective reaction with H atoms.
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| 15. |
- Kumagai, Y., et al.
(författare)
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Impact of Stoichiometry on the Mechanism and Kinetics of Oxidative Dissolution of UO 2 Induced by H 2 O 2 and γ-Irradiation
- 2019
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 123:15, s. 9919-9925
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Tidskriftsartikel (refereegranskat)abstract
- Radiation-induced oxidative dissolution of uranium dioxide (UO 2 ) is one of the most important chemical processes of U driven by redox reactions. We have examined the effect of UO 2 stoichiometry on the oxidative dissolution of UO 2 in aqueous sodium bicarbonate solution induced by hydrogen peroxide (H 2 O 2 ) and γ-ray irradiation. By comparing the reaction kinetics of H 2 O 2 between stoichiometric UO 2.0 and hyper-stoichiometric UO 2.3 , we observed a significant difference in reaction speed and U dissolution kinetics. The stoichiometric UO 2.0 reacted with H 2 O 2 much faster than the hyper-stoichiometric UO 2.3 . The U dissolution from UO 2.0 was initially much lower than that from UO 2.3 but gradually increased as the oxidation by H 2 O 2 proceeded. Increase in the initial H 2 O 2 concentration caused decrease in the U dissolution yield with respect to the H 2 O 2 consumption both for UO 2.0 and UO 2.3 . This decrease in the U dissolution yield is attributed to the catalytic decomposition of H 2 O 2 on the surface of UO 2 . The γ-ray irradiation induced the U dissolution that is analogous to the kinetics by the exposure to a low concentration (2 × 10 -4 mol dm -3 ) of H 2 O 2 . The exposure to higher H 2 O 2 concentrations caused lower U dissolution and resulted in deviation from the U dissolution behavior by γ-ray irradiation.
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| 17. |
- Li, Zhuofeng, et al.
(författare)
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Radiation Chemistry Provides Nanoscopic Insights into the Role of Intermediate Phases in CeO2 Mesocrystal Formation
- 2022
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Ingår i: Angewandte Chemie International Edition. - : Wiley. - 1433-7851 .- 1521-3773. ; 61:6
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Tidskriftsartikel (refereegranskat)abstract
- The role of intermediate phases in CeO2 mesocrystal formation from aqueous CeIII solutions subjected to γ-radiation was studied. Radiolytically formed hydroxyl radicals convert soluble CeIII into less soluble CeIV. Transmission electron microscopy (TEM) and X-ray diffraction studies of samples from different stages of the process allowed the identification of several stages in CeO2 mesocrystal evolution following the oxidation to CeIV: (1) formation of hydrated CeIV hydroxides, serving as intermediates in the liquid-to-solid phase transformation; (2) CeO2 primary particle growth inside the intermediate phase; (3) alignment of the primary particles into “pre-mesocrystals” and subsequently to mesocrystals, guided by confinement of the amorphous intermediate phase and accompanied by the formation of “mineral bridges”. Further alignment of the obtained mesocrystals into supracrystals occurs upon slow drying, making it possible to form complex hierarchical architectures.
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| 18. |
- Loh, Z-H, et al.
(författare)
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Observation of the fastest chemical processes in the radiolysis of water
- 2020
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Ingår i: Science. - : AMER ASSOC ADVANCEMENT SCIENCE. - 0036-8075 .- 1095-9203. ; 367:6474, s. 179-182
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Tidskriftsartikel (refereegranskat)abstract
- Elementary processes associated with ionization of liquid water provide a framework for understanding radiation-matter interactions in chemistry and biology. Although numerous studies have been conducted on the dynamics of the hydrated electron, its partner arising from ionization of liquid water, H2O+, remains elusive. We used tunable femtosecond soft x-ray pulses from an x-ray free electron laser to reveal the dynamics of the valence hole created by strong-field ionization and to track the primary proton transfer reaction giving rise to the formation of OH. The isolated resonance associated with the valence hole (H2O+/OH) enabled straightforward detection. Molecular dynamics simulations revealed that the x-ray spectra are sensitive to structural dynamics at the ionization site. We found signatures of hydrated-electron dynamics in the x-ray spectrum.
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| 19. |
- Nguyen, Son Tien, et al.
(författare)
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Electronic properties of the residual donor in unintentionally doped beta-Ga2O3
- 2016
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Ingår i: Journal of Applied Physics. - : AMER INST PHYSICS. - 0021-8979 .- 1089-7550. ; 120:23
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Tidskriftsartikel (refereegranskat)abstract
- Electron paramagnetic resonance was used to study the donor that is responsible for the n-type conductivity in unintentionally doped (UID) beta-Ga2O3 substrates. We show that in as-grown materials, the donor requires high tempeature annealing to be activated. In partly activated materials with the donor concentration in the 10(16) cm(-3) range or lower, the donor is found to behave as a negative-U center (often called a DX center) with the negative charge state DX- lying similar to 16-20 meV below the neutral charge state d(0) (or E-d), which is estimated to be similar to 28-29 meV below the conduction band minimum. This corresponds to a donor activation energy of E-a similar to 44-49 meV. In fully activated materials with the donor spin density close to similar to 1 x 10(18) cm(-3), donor electrons become delocalized, leading to the formation of impurity bands, which reduces the donor activation energy to E-a similar to 15-17 meV. The results clarify the electronic structure of the dominant donor in UID beta-Ga2O3 and explain the large variation in the previously reported donor activation energy. Published by AIP Publishing.
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| 20. |
- Okuyama, H, et al.
(författare)
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Modifying current-voltage characteristics of a single molecule junction by isotope substitution : OHOD dimer on Cu(110)
- 2012
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Ingår i: Physical Review B. Condensed Matter and Materials Physics. - 1098-0121 .- 1550-235X. ; 85:20
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Tidskriftsartikel (refereegranskat)abstract
- Vibrationally induced configurational change and nonlinear current-voltage (I-V) characteristics are investigated within the scanning tunneling microscope (STM) junction, including hydroxyl dimers on a Cu(110) surface. H-bonded hydroxyl dimers composed of OH and/or OD have a unique inclined geometry that can be switched back and forth by vibrational excitations via the inelastic electron tunneling process of the STM. The relative occupation change between the high-and low-conductance states as a function of bias voltage critically depends on the isotopic compositions, and thus the I-V characteristics can be modified to exhibit negative differential resistance by H/D substitution. The experimental results of the occupation change and I-V curves are nicely reproduced using a recently proposed analytical model combined with comprehensive density functional calculations for the input parameters (vibrational modes and their emission rates by tunneling electrons, conductance, and relative occupation change of high-and low-conductance states), and they underlines the different roles played by the free and shared O-H(D) stretch modes of the hydroxyl dimers on a Cu(110) surface.
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| 23. |
- Schubert, M., et al.
(författare)
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Anisotropy, phonon modes, and free charge carrier parameters in monoclinic beta-gallium oxide single crystals
- 2016
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Ingår i: PHYSICAL REVIEW B. - : AMER PHYSICAL SOC. - 2469-9950. ; 93:12, s. 125209-
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Tidskriftsartikel (refereegranskat)abstract
- We derive a dielectric function tensor model approach to render the optical response of monoclinic and triclinic symmetry materials with multiple uncoupled infrared and far-infrared active modes. We apply our model approach to monoclinic beta-Ga2O3 single-crystal samples. Surfaces cut under different angles from a bulk crystal, (010) and ((2) over bar 01), are investigated by generalized spectroscopic ellipsometry within infrared and far-infrared spectral regions. We determine the frequency dependence of 4 independent beta-Ga2O3 Cartesian dielectric function tensor elements by matching large sets of experimental data using a point-by-point data inversion approach. From matching our monoclinic model to the obtained 4 dielectric function tensor components, we determine all infrared and far-infrared active transverse optic phonon modes with A(u) and B-u symmetry, and their eigenvectors within the monoclinic lattice. We find excellent agreement between our model results and results of density functional theory calculations. We derive and discuss the frequencies of longitudinal optical phonons in beta-Ga2O3. We derive and report density and anisotropic mobility parameters of the free charge carriers within the tin-doped crystals. We discuss the occurrence of longitudinal phonon plasmon coupled modes in beta-Ga2O3 and provide their frequencies and eigenvectors. We also discuss and present monoclinic dielectric constants for static electric fields and frequencies above the reststrahlen range, and we provide a generalization of the Lyddane-Sachs-Teller relation for monoclinic lattices with infrared and far-infrared active modes. We find that the generalized Lyddane-Sachs-Teller relation is fulfilled excellently for beta-Ga2O3.
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| 24. |
- Sopena Moros, Arturo, et al.
(författare)
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Tracking Cavity Formation in Electron Solvation : Insights from X-ray Spectroscopy and Theory
- 2024
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 146:5, s. 3262-3269
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Tidskriftsartikel (refereegranskat)abstract
- We present time-resolved X-ray absorption spectra of ionized liquid water and demonstrate that OH radicals, H3O+ ions, and solvated electrons all leave distinct X-ray-spectroscopic signatures. Particularly, this allows us to characterize the electron solvation process through a tool that focuses on the electronic response of oxygen atoms in the immediate vicinity of a solvated electron. Our experimental results, supported by ab initio calculations, confirm the formation of a cavity in which the solvated electron is trapped. We show that the solvation dynamics are governed by the magnitude of the random structural fluctuations present in water. As a consequence, the solvation time is highly sensitive to temperature and to the specific way the electron is injected into water.
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