| 1. |
- Östrom, Henrik, et al.
(författare)
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Probing the transition state region in catalytic CO oxidation on Ru
- 2015
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Ingår i: Science. - : American Association for the Advancement of Science (AAAS). - 0036-8075 .- 1095-9203. ; 347:6225, s. 978-982
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Tidskriftsartikel (refereegranskat)abstract
- Femtosecond x-ray laser pulses are used to probe the carbon monoxide (CO) oxidation reaction on ruthenium (Ru) initiated by an optical laser pulse. On a time scale of a few hundred femtoseconds, the optical laser pulse excites motions of CO and oxygen (O) on the surface, allowing the reactants to collide, and, with a transient close to a picosecond (ps), new electronic states appear in the OK-edge x-ray absorption spectrum. Density functional theory calculations indicate that these result from changes in the adsorption site and bond formation between CO and O with a distribution of OC-O bond lengths close to the transition state (TS). After 1 ps, 10% of the CO populate the TS region, which is consistent with predictions based on a quantum oscillator model.
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| 2. |
- Sellberg, Jonas A., et al.
(författare)
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Ultrafast X-ray probing of water structure below the homogeneous ice nucleation temperature
- 2014
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Ingår i: Nature. - : Springer Science and Business Media LLC. - 0028-0836 .- 1476-4687. ; 510:7505, s. 381-
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Tidskriftsartikel (refereegranskat)abstract
- Water has a number of anomalous physical properties, and some of these become drastically enhanced on supercooling below the freezing point. Particular interest has focused on thermodynamic response functions that can be described using a normal component and an anomalous component that seems to diverge at about 228 kelvin (refs 1-3). This has prompted debate about conflicting theories(4-12) that aim to explain many of the anomalous thermodynamic properties of water. One popular theory attributes the divergence to a phase transition between two forms of liquid water occurring in the 'no man's land' that lies below the homogeneous ice nucleation temperature (T-H) at approximately 232 kelvin(13) and above about 160 kelvin(14), and where rapid ice crystallization has prevented any measurements of the bulk liquid phase. In fact, the reliable determination of the structure of liquid water typically requires temperatures above about 250 kelvin(2,15). Water crystallization has been inhibited by using nanoconfinement(16), nanodroplets(17) and association with biomolecules(16) to give liquid samples at temperatures below T-H, but such measurements rely on nanoscopic volumes of water where the interaction with the confining surfaces makes the relevance to bulk water unclear(18). Here we demonstrate that femtosecond X-ray laser pulses can be used to probe the structure of liquid water in micrometre-sized droplets that have been evaporatively cooled(19-21) below TH. We find experimental evidence for the existence of metastable bulk liquid water down to temperatures of 227(-1)(+2) kelvin in the previously largely unexplored no man's land. We observe a continuous and accelerating increase in structural ordering on supercooling to approximately 229 kelvin, where the number of droplets containing ice crystals increases rapidly. But a few droplets remain liquid for about a millisecond even at this temperature. The hope now is that these observations and our detailed structural data will help identify those theories that best describe and explain the behaviour of water.
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| 3. |
- Xin, H., et al.
(författare)
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Strong Influence of Coadsorbate Interaction on CO Desorption Dynamics on Ru(0001) Probed by Ultrafast X-Ray Spectroscopy and Ab Initio Simulations
- 2015
-
Ingår i: Physical Review Letters. - 0031-9007 .- 1079-7114. ; 114:15
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Tidskriftsartikel (refereegranskat)abstract
- We show that coadsorbed oxygen atoms have a dramatic influence on the CO desorption dynamics from Ru(0001). In contrast to the precursor-mediated desorption mechanism on Ru(0001), the presence of surface oxygen modifies the electronic structure of Ru atoms such that CO desorption occurs predominantly via the direct pathway. This phenomenon is directly observed in an ultrafast pump-probe experiment using a soft x-ray free-electron laser to monitor the dynamic evolution of the valence electronic structure of the surface species. This is supported with the potential of mean force along the CO desorption path obtained from density-functional theory calculations. Charge density distribution and frozen-orbital analysis suggest that the oxygen-induced reduction of the Pauli repulsion, and consequent increase of the dative interaction between the CO 5 sigma and the charged Ru atom, is the electronic origin of the distinct desorption dynamics. Ab initio molecular dynamics simulations of CO desorption from Ru(0001) and oxygen-coadsorbed Ru(0001) provide further insights into the surface bond-breaking process.
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| 4. |
- Beye, M., et al.
(författare)
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Selective Ultrafast Probing of Transient Hot Chemisorbed and Precursor States of CO on Ru(0001)
- 2013
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Ingår i: Physical Review Letters. - 0031-9007 .- 1079-7114. ; 110:18
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Tidskriftsartikel (refereegranskat)abstract
- We have studied the femtosecond dynamics following optical laser excitation of CO adsorbed on a Ru surface by monitoring changes in the occupied and unoccupied electronic structure using ultrafast soft x-ray absorption and emission. We recently reported [M. Dell'Angela et al. Science 339, 1302 (2013)] a phonon-mediated transition into a weakly adsorbed precursor state occurring on a time scale of >2 ps prior to desorption. Here we focus on processes within the first picosecond after laser excitation and show that the metal-adsorbate coordination is initially increased due to hot-electron-driven vibrational excitations. This process is faster than, but occurs in parallel with, the transition into the precursor state. With resonant x-ray emission spectroscopy, we probe each of these states selectively and determine the respective transient populations depending on optical laser fluence. Ab initio molecular dynamics simulations of CO adsorbed on Ru(0001) were performed at 1500 and 3000 K providing insight into the desorption process.
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| 5. |
- Dell'Angela, M., et al.
(författare)
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Real-Time Observation of Surface Bond Breaking with an X-ray Laser
- 2013
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Ingår i: Science. - : American Association for the Advancement of Science (AAAS). - 0036-8075 .- 1095-9203. ; 339:6125, s. 1302-1305
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Tidskriftsartikel (refereegranskat)abstract
- We used the Linac Coherent Light Source free-electron x-ray laser to probe the electronic structure of CO molecules as their chemisorption state on Ru(0001) changes upon exciting the substrate by using a femtosecond optical laser pulse. We observed electronic structure changes that are consistent with a weakening of the CO interaction with the substrate but without notable desorption. A large fraction of the molecules (30%) was trapped in a transient precursor state that would precede desorption. We calculated the free energy of the molecule as a function of the desorption reaction coordinate using density functional theory, including van der Waals interactions. Two distinct adsorption wells-chemisorbed and precursor state separated by an entropy barrier-explain the anomalously high prefactors often observed in desorption of molecules from metals.
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| 6. |
- Hellmann, S., et al.
(författare)
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Time-resolved x-ray photoelectron spectroscopy at FLASH
- 2012
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Ingår i: New Journal of Physics. - : IOP Publishing. - 1367-2630. ; 14
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Tidskriftsartikel (refereegranskat)abstract
- The technique of time-resolved pump-probe x-ray photoelectron spectroscopy using the free-electron laser in Hamburg (FLASH) is described in detail. Particular foci lie on the macrobunch resolving detection scheme, the role of vacuum space-charge effects and the synchronization of pump and probe lasers. In an exemplary case study, the complete Ta 4f core-level dynamics in the layered charge-density-wave (CDW) compound 1T-TaS2 in response to impulsive optical excitation is measured on the sub-picosecond to nanosecond timescale. The observed multi-component dynamics is related to the intrinsic melting and reformation of the CDW as well as to extrinsic pump-laser-induced vacuum space-charge effects.
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| 7. |
- Hellmann, S., et al.
(författare)
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Ultrafast Melting of a Charge-Density Wave in the Mott Insulator 1T-TaS2
- 2010
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Ingår i: Physical Review Letters. - 1079-7114. ; 105:18
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Tidskriftsartikel (refereegranskat)abstract
- Femtosecond time-resolved core-level photoemission spectroscopy with a free-electron laser is used to measure the atomic-site specific charge-order dynamics of the charge-density wave in the Mott insulator 1T-TaS2. After strong photoexcitation, a prompt loss of charge order and subsequent fast equilibration dynamics of the electron-lattice system are observed. On the time scale of electron-phonon thermalization, about 1 ps, the system is driven across a phase transition from a long-range charge ordered state to a quasiequilibrium state with domainlike short-range charge and lattice order. The experiment opens the way to study the nonequilibrium dynamics of condensed matter systems with full elemental, chemical, and atomic-site selectivity.
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| 8. |
- LaRue, Jerry, et al.
(författare)
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Real-Time Elucidation of Catalytic Pathways in CO Hydrogenation on Ru
- 2017
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Ingår i: The Journal of Physical Chemistry Letters. - : American Chemical Society (ACS). - 1948-7185. ; 8:16, s. 3820-3825
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Tidskriftsartikel (refereegranskat)abstract
- The direct elucidation of the reaction pathways in heterogeneous catalysis has been challenging due to the short-lived nature of reaction intermediates. Here, we directly measured on ultrafast time scales the initial hydrogenation steps of adsorbed CO on a Ru catalyst surface, which is known as the bottleneck reaction in syngas and CO2 reforming processes. We initiated the hydrogenation of CO with an ultrafast laser temperature jump and probed transient changes in the electronic structure using real-time X-ray spectroscopy. In combination with theoretical simulations, we verified the formation of CHO during CO hydrogenation.
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| 9. |
- Öberg, Henrik, et al.
(författare)
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Optical laser-induced CO desorption from Ru(0001) monitored with a free-electron X-ray laser : DFT prediction and X-ray confirmation of a precursor state
- 2015
-
Ingår i: Surface Science. - : Elsevier BV. - 0039-6028 .- 1879-2758. ; 640, s. 80-88
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Tidskriftsartikel (refereegranskat)abstract
- We present density functional theory modeling of time-resolved optical pump/X-ray spectroscopic probe data of CO desorption from Ru(0001). The BEEF van der Waals functional predicts a weakly bound state as a precursor to desorption. The optical pump leads to a near-instantaneous (<100 fs) increase of the electronic temperature to nearly 7000 K. The temperature evolution and energy transfer between electrons, substrate phonons and adsorbate is described by the two-temperature model and found to equilibrate on a timescale of a few picoseconds to an elevated local temperature of similar to 2000K. Estimating the free energy based on the computed potential of mean force along the desorption path, we find an entropic barrier to desorption (and by time-reversal also to adsorption). This entropic barrier separates the chemisorbed and precursor states, and becomes significant at the elevated temperature of the experiment (similar to 1.4 eV at 2000 K). Experimental pump-probe X-ray absorption/X-ray emission spectroscopy indicates population of a precursor state to desorption upon laser-excitation of the system (Dell'Angela et al., 2013). Computing spectra along the desorption path confirms the picture of a weakly bound transient state arising from ultrafast heating of the metal substrate.
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| 10. |
- Chen, Z., et al.
(författare)
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Ultrafast Self-Induced X-Ray Transparency and Loss of Magnetic Diffraction
- 2018
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Ingår i: Physical Review Letters. - : AMER PHYSICAL SOC. - 0031-9007 .- 1079-7114. ; 121:13
-
Tidskriftsartikel (refereegranskat)abstract
- Using ultrafast similar or equal to 2.5 fs and similar or equal to 25 fs self-amplified spontaneous emission pulses of increasing intensity and a novel experimental scheme, we report the concurrent increase of stimulated emission in the forward direction and loss of out-of-beam diffraction contrast for a Co/Pd multilayer sample. The experimental results are quantitatively accounted for by a statistical description of the pulses in conjunction with the optical Bloch equations. The dependence of the stimulated sample response on the incident intensity, coherence time, and energy jitter of the employed pulses reveals the importance of increased control of x-ray free electron laser radiation.
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| 11. |
- Dell'Angela, M., et al.
(författare)
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Vacuum space charge effects in sub-picosecond soft X-ray photoemission on a molecular adsorbate layer
- 2015
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Ingår i: Structural Dynamics. - : AIP Publishing. - 2329-7778. ; 2:2
-
Tidskriftsartikel (refereegranskat)abstract
- Vacuum space charge induced kinetic energy shifts of O 1s and Ru 3d core levels in femtosecond soft X-ray photoemission spectra (PES) have been studied at a free electron laser (FEL) for an oxygen layer on Ru(0001). We fully reproduced the measurements by simulating the in-vacuum expansion of the photoelectrons and demonstrate the space charge contribution of the high-order harmonics in the FEL beam. Employing the same analysis for 400 nm pump-X-ray probe PES, we can disentangle the delay dependent Ru 3d energy shifts into effects induced by space charge and by lattice heating from the femtosecond pump pulse.
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| 12. |
- Grånäs, Oscar, 1979-, et al.
(författare)
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Ultrafast modification of the electronic structure of a correlated insulator
- 2022
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Ingår i: Physical Review Research. - : American Physical Society. - 2643-1564. ; 4:3
-
Tidskriftsartikel (refereegranskat)abstract
- A nontrivial balance between Coulomb repulsion and kinematic effects determines the electronic structure of correlated electron materials. The use of electromagnetic fields strong enough to rival these native microscopic interactions allows us to study the electronic response as well as the time scales and energies involved in using quantum effects for possible applications. We use element-specific transient x-ray absorption spectroscopy and high-harmonic generation to measure the response to ultrashort off-resonant optical fields in the prototypical correlated electron insulator NiO. Surprisingly, fields of up to 0.22 V/angstrom lead to no detectable changes in the correlated Ni 3d orbitals contrary to previous predictions. A transient directional charge transfer is uncovered, a behavior that is captured by first-principles theory. Our results highlight the importance of retardation effects in electronic screening and pinpoints a key challenge in functionalizing correlated materials for ultrafast device operation.
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| 13. |
- Kunnus, K., et al.
(författare)
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Identification of the dominant photochemical pathways and mechanistic insights to the ultrafast ligand exchange of Fe(CO)(5) to Fe(CO)(4)EtOH
- 2016
-
Ingår i: Structural Dynamics. - : AIP Publishing. - 2329-7778. ; 3:4
-
Tidskriftsartikel (refereegranskat)abstract
- We utilized femtosecond time-resolved resonant inelastic X-ray scattering and ab initio theory to study the transient electronic structure and the photoinduced molecular dynamics of a model metal carbonyl photocatalyst Fe(CO)(5) in ethanol solution. We propose mechanistic explanation for the parallel ultrafast intra-molecular spin crossover and ligation of the Fe(CO)(4) which are observed following a charge transfer photoexcitation of Fe(CO)(5) as reported in our previous study [ Wernet et al., Nature 520, 78 (2015)]. We find that branching of the reaction pathway likely happens in the (1)A(1) state of Fe(CO)(4). A sub-picosecond time constant of the spin crossover from B-1(2) to B-3(2) is rationalized by the proposed B-1(2) -> (1)A(1) -> B-3(2) mechanism. Ultrafast ligation of the B-1(2) Fe(CO)(4) state is significantly faster than the spin-forbidden and diffusion limited ligation process occurring from the B-3(2) Fe(CO)(4) ground state that has been observed in the previous studies. We propose that the ultrafast ligation occurs via B-1(2) -> (1)A(1) -> (1)A'Fe(CO)(4)EtOH pathway and the time scale of the (1)A(1) Fe(CO)(4) state ligation is governed by the solute-solvent collision frequency. Our study emphasizes the importance of understanding the interaction of molecular excited states with the surrounding environment to explain the relaxation pathways of photoexcited metal carbonyls in solution.
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| 14. |
- Nilsson, Anders, et al.
(författare)
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Catalysis in real time using X-ray lasers
- 2017
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Ingår i: Chemical Physics Letters. - : Elsevier BV. - 0009-2614 .- 1873-4448. ; 675, s. 145-173
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Tidskriftsartikel (refereegranskat)abstract
- We describe how the unique temporal and spectral characteristics of X-ray free-electron lasers (XFEL) can be utilized to follow chemical transformations in heterogeneous catalysis in real time. We highlight the systematic study of CO oxidation on Ru(0001), which we initiate either using a femtosecond pulse from an optical laser or by activating only the oxygen atoms using a THz pulse. We find that CO is promoted into an entropy-controlled precursor state prior to desorbing when the surface is heated in the absence of oxygen, whereas in the presence of oxygen, CO desorbs directly into the gas phase. We monitor the activation of atomic oxygen explicitly by the reduced split between bonding and antibonding orbitals as the oxygen comes out of the strongly bound hollow position. Applying these novel XFEL techniques to the full oxidation reaction resulted in the surprising observation of a significant fraction of the reactants at the transition state through the electronic signature of the new bond formation.
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| 15. |
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| 16. |
- Beye, M, et al.
(författare)
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Nestmate recognition and the genetic relatedness of nests in the ant Formica pratensis
- 1998
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Ingår i: BEHAVIORAL ECOLOGY AND SOCIOBIOLOGY. - : SPRINGER VERLAG. - 0340-5443. ; 43:1, s. 67-72
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Tidskriftsartikel (övrigt vetenskapligt/konstnärligt)abstract
- Genetic relatedness of the mound-building ant Formica pratensis was determined by means of microsatellite DNA polymorphism, and its impact on nestmate recognition was tested in a population in Southern Sweden (Oeland), Recognition between nests was measur
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| 17. |
- Katayama, T., et al.
(författare)
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Ultrafast soft X-ray emission spectroscopy of surface adsorbates using an X-ray free electron laser
- 2013
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Ingår i: Journal of Electron Spectroscopy and Related Phenomena. - : Elsevier BV. - 0368-2048 .- 1873-2526. ; 187, s. 9-14
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Tidskriftsartikel (refereegranskat)abstract
- We report on an experimental system designed to probe chemical reactions on solid surfaces on a sub-picosecond timescale using soft X-ray emission spectroscopy at the Linac Coherent Light Source (LCLS) free electron laser (FEL) at the SLAC National Accelerator Laboratory. We analyzed the O 1s X-ray emission spectra recorded from atomic oxygen adsorbed on a Ru(0001) surface at a synchrotron beamline (SSRL, BL13-2) and an FEL beamline (LCLS, SXR). We have demonstrated conditions that provide negligible amount of FEL induced damage of the sample. In addition we show that the setup is capable of tracking the temporal evolution of electronic structure during a surface reaction of submonolayer quantities of CO molecules desorbing from the surface.
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| 18. |
- Laksmono, Hartawan, et al.
(författare)
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Anomalous Behavior of the Homogeneous Ice Nucleation Rate in No-Man's Land
- 2015
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Ingår i: The Journal of Physical Chemistry Letters. - : American Chemical Society (ACS). - 1948-7185. ; 6:14, s. 2826-2832
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Tidskriftsartikel (refereegranskat)abstract
- We present an analysis of ice nucleation kinetics from near-ambient pressure water as temperature decreases below the homogeneous limit T-H by cooling micrometer-sized droplets (microdroplets) evaporatively at 10(3)-10(4) K/s and probing the structure ultrafast using femtosecond pulses from the Linac Coherent Light Source (LCLS) free-electron X-ray laser. Below 232 K, we observed a slower nucleation rate increase with decreasing temperature than anticipated from previous measurements, which we suggest is due to the rapid decrease in water's diffusivity. This is consistent with earlier findings that microdroplets do not crystallize at <227 K, but vitrify at cooling rates of 10(6)-10(7) K/s. We also hypothesize that the slower increase in the nucleation rate is connected with the proposed fragile-to-strong transition anomaly in water.
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| 19. |
- Leitner, T., et al.
(författare)
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Time-resolved electron spectroscopy for chemical analysis of photodissociation : Photoelectron spectra of Fe(CO)(5), Fe(CO)(4), and Fe(CO)(3)
- 2018
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Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 149:4
-
Tidskriftsartikel (refereegranskat)abstract
- The prototypical photoinduced dissociation of Fe(CO)(5) 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)(5) successively dissociates to Fe(CO)(4) and Fe(CO)(3) along a pathway where both fragments retain the singlet multiplicity of Fe(CO)(5). The x-ray free-electron laser FLASH is used to probe the reaction intermediates Fe(CO)(4) and Fe(CO)(3) 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 valenceorbital interactions upon Fe-CO dissociation, thereby validating fundamental theoretical concepts in Fe-CO bonding. Chemical shifts of CO 3 sigma inner-valence and Fe 3 sigma 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 howcharge and spin density changes in molecular dissociation and excited-state dynamics are expressed in valence and core-level photoelectron spectroscopy. Published by AIP Publishing.
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| 20. |
- Schönhense, G., et al.
(författare)
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Suppression of the vacuum space-charge effect in fs-photoemission by a retarding electrostatic front lens
- 2021
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Ingår i: Review of Scientific Instruments. - : American Institute of Physics (AIP). - 0034-6748 .- 1089-7623. ; 92:5
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Tidskriftsartikel (refereegranskat)abstract
- The performance of time-resolved photoemission experiments at fs-pulsed photon sources is ultimately limited by the e-e Coulomb interaction, downgrading energy and momentum resolution. Here, we present an approach to effectively suppress space-charge artifacts in momentum microscopes and photoemission microscopes. A retarding electrostatic field generated by a special objective lens repels slow electrons, retaining the k-image of the fast photoelectrons. The suppression of space-charge effects scales with the ratio of the photoelectron velocities of fast and slow electrons. Fields in the range from -20 to -1100 V/mm for E-kin = 100 eV to 4 keV direct secondaries and pump-induced slow electrons back to the sample surface. Ray tracing simulations reveal that this happens within the first 40 to 3 mu m above the sample surface for E-kin = 100 eV to 4 keV. An optimized front-lens design allows switching between the conventional accelerating and the new retarding mode. Time-resolved experiments at E-kin = 107 eV using fs extreme ultraviolet probe pulses from the free-electron laser FLASH reveal that the width of the Fermi edge increases by just 30 meV at an incident pump fluence of 22 mJ/cm(2) (retarding field -21 V/mm). For an accelerating field of +2 kV/mm and a pump fluence of only 5 mJ/cm(2), it increases by 0.5 eV (pump wavelength 1030 nm). At the given conditions, the suppression mode permits increasing the slow-electron yield by three to four orders of magnitude. The feasibility of the method at high energies is demonstrated without a pump beam at E-kin = 3830 eV using hard x rays from the storage ring PETRA III. The approach opens up a previously inaccessible regime of pump fluences for photoemission experiments.
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| 21. |
- Wernet, Ph., et al.
(författare)
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Communication : Direct evidence for sequential dissociation of gas-phase Fe(CO)(5) via a singlet pathway upon excitation at 266 nm
- 2017
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Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 146:21
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Tidskriftsartikel (refereegranskat)abstract
- We prove the hitherto hypothesized sequential dissociation of Fe(CO)(5) in the gas phase upon photoexcitation at 266 nm via a singlet pathway with time-resolved valence and core-level photoelectron spectroscopy with an x-ray free-electron laser. Valence photoelectron spectra are used to identify free CO molecules and to determine the time constants of stepwise dissociation to Fe(CO)(4) within the temporal resolution of the experiment and further to Fe(CO)(3) within 3 ps. Fe 3p core-level photoelectron spectra directly reflect the singlet spin state of the Fe center in Fe(CO)(5), Fe(CO)(4), and Fe(CO)(3) showing that the dissociation exclusively occurs along a singlet pathway without triplet-state contribution. Our results are important for assessing intra- and intermolecular relaxation processes in the photodissociation dynamics of the prototypical Fe(CO)(5) complex in the gas phase and in solution, and they establish time-resolved core-level photoelectron spectroscopy as a powerful tool for determining the multiplicity of transition metals in photochemical reactions of coordination complexes.
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| 22. |
- Beye, Martin, et al.
(författare)
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Chemical Bond Activation Observed with an X-ray Laser
- 2016
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Ingår i: The Journal of Physical Chemistry Letters. - : American Chemical Society (ACS). - 1948-7185. ; 7:18, s. 3647-3651
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Tidskriftsartikel (refereegranskat)abstract
- The concept of bonding and antibonding orbitals is fundamental in chemistry. The population of those orbitals and the energetic difference between the two reflect the strength of the bonding interaction. Weakening the bond is expected to reduce this energetic splitting, but the transient character of bond-activation has so far prohibited direct experimental access. Here we apply time-resolved soft X-ray spectroscopy at a free electron laser to directly observe the decreased bonding antibonding splitting following bond-activation using an ultrashort optical laser pulse.
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| 23. |
- Engel, Robin Y., et al.
(författare)
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Electron population dynamics in resonant non-linear x-ray absorption in nickel at a free-electron laser
- 2023
-
Ingår i: Structural Dynamics. - : American Institute of Physics (AIP). - 2329-7778. ; 10:5
-
Tidskriftsartikel (refereegranskat)abstract
- Free-electron lasers provide bright, ultrashort, and monochromatic x-ray pulses, enabling novel spectroscopic measurements not only with femtosecond temporal resolution: The high fluence of their x-ray pulses can also easily enter the regime of the non-linear x-ray-matter interaction. Entering this regime necessitates a rigorous analysis and reliable prediction of the relevant non-linear processes for future experiment designs. Here, we show non-linear changes in the L-3-edge absorption of metallic nickel thin films, measured with fluences up to 60 J/cm(2). We present a simple but predictive rate model that quantitatively describes spectral changes based on the evolution of electronic populations within the pulse duration. Despite its simplicity, the model reaches good agreement with experimental results over more than three orders of magnitude in fluence, while providing a straightforward understanding of the interplay of physical processes driving the non-linear changes. Our findings provide important insights for the design and evaluation of future high-fluence free-electron laser experiments and contribute to the understanding of non-linear electron dynamics in x-ray absorption processes in solids at the femtosecond timescale.
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| 24. |
- Jay, Raphael M., et al.
(författare)
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Disentangling Transient Charge Density and Metal-Ligand Covalency in Photoexcited Ferricyanide with Femtosecond Resonant Inelastic Soft X-ray Scattering
- 2018
-
Ingår i: The Journal of Physical Chemistry Letters. - : American Chemical Society (ACS). - 1948-7185. ; 9:12, s. 3538-3543
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Tidskriftsartikel (refereegranskat)abstract
- Soft X-ray spectroscopies are ideal probes of the local valence electronic structure of photocatalytically active metal sites. Here, we apply the selectivity of time resolved resonant inelastic X-ray scattering at the iron L-edge to the transient charge distribution of an optically excited charge-transfer state in aqueous ferricyanide. Through comparison to steady-state spectra and quantum chemical calculations, the coupled effects of valence-shell closing and ligand-hole creation are experimentally and theoretically disentangled and described in terms of orbital occupancy, metal-ligand covalency, and ligand field splitting, thereby extending established steady-state concepts to the excited-state domain. pi-Back-donation is found to be mainly determined by the metal site occupation, whereas the ligand hole instead influences sigma-donation. Our results demonstrate how ultrafast resonant inelastic X-ray scattering can help characterize local charge distributions around catalytic metal centers in short-lived charge-transfer excited states, as a step toward future rationalization and tailoring of photocatalytic capabilities of transition-metal complexes.
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| 25. |
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| 26. |
- Schreck, Simon, et al.
(författare)
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Atom-specific activation in CO oxidation
- 2018
-
Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 149:23
-
Tidskriftsartikel (refereegranskat)abstract
- We report on atom-specific activation of CO oxidation on Ru(0001) via resonant X-ray excitation. We show that resonant 1s core-level excitation of atomically adsorbed oxygen in the co-adsorbed phase of CO and oxygen directly drives CO oxidation. We separate this direct resonant channel from indirectly driven oxidation via X-ray induced substrate heating. Based on density functional theory calculations, we identify the valence-excited state created by the Auger decay as the driving electronic state for direct CO oxidation. We utilized the fresh-slice multi-pulse mode at the Linac Coherent Light Source that provided time-overlapped and 30 fs delayed pairs of soft X-ray pulses and discuss the prospects of femtosecond X-ray pump X-ray spectroscopy probe, as well as X-ray two-pulse correlation measurements for fundamental investigations of chemical reactions via selective X-ray excitation.
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| 27. |
- Schreck, Simon, et al.
(författare)
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Reabsorption of Soft X-Ray Emission at High X-Ray Free-Electron Laser Fluences
- 2014
-
Ingår i: Physical Review Letters. - 0031-9007 .- 1079-7114. ; 113:15, s. 153002-
-
Tidskriftsartikel (refereegranskat)abstract
- We report on oxygen K-edge soft x-ray emission spectroscopy from a liquid water jet at the Linac Coherent Light Source. We observe significant changes in the spectral content when tuning over a wide range of incident x-ray fluences. In addition the total emission yield decreases at high fluences. These modifications result from reabsorption of x-ray emission by valence-excited molecules generated by the Auger cascade. Our observations have major implications for future x-ray emission studies at intense x-ray sources. We highlight the importance of the x-ray pulse length with respect to the core-hole lifetime.
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| 28. |
- Sellberg, Jonas A., et al.
(författare)
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X-ray emission spectroscopy of bulk liquid water in no-man's land
- 2015
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Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 142:4
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Tidskriftsartikel (refereegranskat)abstract
- The structure of bulk liquid water was recently probed by x-ray scattering below the temperature limit of homogeneous nucleation (T-H) of similar to 232 K [J. A. Sellberg et al., Nature 510, 381-384 (2014)]. Here, we utilize a similar approach to study the structure of bulk liquid water below T-H using oxygen K-edge x-ray emission spectroscopy (XES). Based on previous XES experiments [T. Tokushima et al., Chem. Phys. Lett. 460, 387-400 (2008)] at higher temperatures, we expected the ratio of the 1b(1)' and 1b(1) peaks associated with the lone-pair orbital in water to change strongly upon deep supercooling as the coordination of the hydrogen (H-) bonds becomes tetrahedral. In contrast, we observed only minor changes in the lone-pair spectral region, challenging an interpretation in terms of two interconverting species. A number of alternative hypotheses to explain the results are put forward and discussed. Although the spectra can be explained by various contributions from these hypotheses, we here emphasize the interpretation that the line shape of each component changes dramatically when approaching lower temperatures, where, in particular, the peak assigned to the proposed disordered component would become more symmetrical as vibrational interference becomes more important.
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| 29. |
- Thielemann-Kühn, Nele, et al.
(författare)
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Optical control of 4f orbital state in rare-earth metals
- 2024
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Ingår i: Science Advances. - : American Association for the Advancement of Science (AAAS). - 2375-2548. ; 10:16
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Tidskriftsartikel (refereegranskat)abstract
- A change of orbital state alters the coupling between ions and their surroundings drastically. Orbital excitations are hence key to understand and control interaction of ions. Rare-earth elements with strong magneto-crystalline anisotropy (MCA) are important ingredients for magnetic devices. Thus, control of their localized 4f magnetic moments and anisotropy is one major challenge in ultrafast spin physics. With time-resolved x-ray absorption and resonant inelastic scattering experiments, we show for Tb metal that 4f-electronic excitations out of the ground-state multiplet occur after optical pumping. These excitations are driven by inelastic 5d-4f-electron scattering, altering the 4f-orbital state and consequently the MCA with important implications for magnetization dynamics in 4f-metals and more general for the excitation of localized electronic states in correlated materials.
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| 30. |
- Wang, Hsin-Yi, et al.
(författare)
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Time-resolved observation of transient precursor state of CO on Ru(0001) using carbon K-edge spectroscopy
- 2020
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - 1463-9076 .- 1463-9084. ; 22:5, s. 2677-2684
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Tidskriftsartikel (refereegranskat)abstract
- The transient dynamics of carbon monoxide (CO) molecules on a Ru(0001) surface following femtosecond optical laser pump excitation has been studied by monitoring changes in the unoccupied electronic structure using an ultrafast X-ray free-electron laser (FEL) probe. The particular symmetry of perpendicularly chemisorbed CO on the surface is exploited to investigate how the molecular orientation changes with time by varying the polarization of the FEL pulses. The time evolution of spectral features corresponding to the desorption precursor state was well distinguished due to the narrow line-width of the C K-edge in the X-ray absorption (XA) spectrum, illustrating that CO molecules in the precursor state rotated freely and resided on the surface for several picoseconds. Most of the CO molecules trapped in the precursor state ultimately cooled back down to the chemisorbed state, while we estimate that ∼14.5 ± 4.9% of the molecules in the precursor state desorbed into the gas phase. It was also observed that chemisorbed CO molecules diffused over the metal surface from on-top sites toward highly coordinated sites. In addition, a new “vibrationally hot precursor” state was identified in the polarization-dependent XA spectra.
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| 31. |
- Wernet, Philippe, et al.
(författare)
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Mapping chemical bonding of reaction intermediates with femtosecond X-ray laser spectroscopy
- 2013
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Ingår i: XVIIIth International Conference on Ultrafast Phenomena. - : EDP Sciences. - 9782759809561 ; , s. 05025-
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Konferensbidrag (övrigt vetenskapligt/konstnärligt)abstract
- We determine the pathways in the photo-dissociation reactions of Fe(CO)5 both in the gas phase and in solution by mapping the valence electronic structure of the reaction intermediates with femtosecond X-ray laser spectroscopy.
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| 32. |
- Wernet, Philippe, 1971-, et al.
(författare)
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Orbital-specific mapping of the ligand exchange dynamics of Fe(CO)5 in solution
- 2015
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Ingår i: Nature. - : Springer Science and Business Media LLC. - 0028-0836 .- 1476-4687. ; 520:7545, s. 78-81
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Tidskriftsartikel (refereegranskat)abstract
- Transition-metal complexes have long attracted interest for fundamental chemical reactivity studies and possible use in solar energy conversion. Electronic excitation, ligand loss from the metal centre, or a combination of both, creates changes in charge and spin density at the metal site that need to be controlled to optimize complexes for photocatalytic hydrogen production and selective carbon-hydrogen bond activation. An understanding at the molecular level of how transition-metal complexes catalyse reactions, and in particular of the role of the short-lived and reactive intermediate states involved, will be critical for such optimization. However, suitable methods for detailed characterization of electronic excited states have been lacking. Here we show, with the use of X-ray laser-based femtosecond resolution spectroscopy and advanced quantum chemical theory to probe the reaction dynamics of the benchmark transition-metal complex Fe(CO)5 insolution, that the photoinduced removal of CO generates the 16-electron Fe(CO)4 species, a homogeneous catalyst with an electron deficiency at the Fe centre, in a hitherto unreported excited singlet state that either converts to the triplet ground state or combines with a CO or solvent molecule to regenerate a penta-coordinated Fe species on a sub-picosecond timescale. This finding, which resolves the debate about the relative importance of different spin channels in the photochemistry of Fe(CO)5 (refs 4, 16,17,18,19 and 20), was made possible by the ability of femtosecond X-ray spectroscopy to probe frontier-orbital interactions with atom specificity. We expect the method to be broadly applicable in the chemical sciences, and to complement approaches that probe structural dynamics in ultrafast processes.
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