| 1. |
- 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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| 2. |
- 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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| 3. |
- 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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| 4. |
- 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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| 5. |
- 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
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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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| 6. |
- 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
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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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| 7. |
- Sousa, O. M., et al.
(författare)
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Pressure effect on the structural, electronic, and magnetic properties of the battery cathode material LiMn2O4 : An ab-initio study
- 2023
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Ingår i: Journal of Physics and Chemistry of Solids. - : Elsevier. - 0022-3697 .- 1879-2553. ; 175
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Tidskriftsartikel (refereegranskat)abstract
- LiMn2O4 is a battery cathode material with desirable properties such as low cost, low toxicity, high natural abundance of Mn, and environmental compatibility. By means of first-principles calculations, we study the structural, magnetic, and electronic properties of LiMn2O4 under ambient conditions and high hydrostatic pressures (until 20 GPa). We obtain two oxidation states for Mn, even using a cubic structure, which differ in all analyzed properties: structural, electronic, and magnetic. At P > 0, such properties were found to display a standard behavior decreasing smoothly and linearly with pressure. Furthermore, the enthalpy of cubic and orthorhombic structures under low and high-pressure conditions were examined, showing that no cubic to orthorhombic phase transition exists in all the investigated pressure range, nor is a magnetic cubic to a non-magnetic cubic phase transition possible.
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| 8. |
- 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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| 9. |
- Custodio, TF, et al.
(författare)
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Selection, biophysical and structural analysis of synthetic nanobodies that effectively neutralize SARS-CoV-2
- 2020
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Ingår i: Nature communications. - : Springer Science and Business Media LLC. - 2041-1723. ; 11:1, s. 5588-
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Tidskriftsartikel (refereegranskat)abstract
- The coronavirus SARS-CoV-2 is the cause of the ongoing COVID-19 pandemic. Therapeutic neutralizing antibodies constitute a key short-to-medium term approach to tackle COVID-19. However, traditional antibody production is hampered by long development times and costly production. Here, we report the rapid isolation and characterization of nanobodies from a synthetic library, known as sybodies (Sb), that target the receptor-binding domain (RBD) of the SARS-CoV-2 spike protein. Several binders with low nanomolar affinities and efficient neutralization activity were identified of which Sb23 displayed high affinity and neutralized pseudovirus with an IC50 of 0.6 µg/ml. A cryo-EM structure of the spike bound to Sb23 showed that Sb23 binds competitively in the ACE2 binding site. Furthermore, the cryo-EM reconstruction revealed an unusual conformation of the spike where two RBDs are in the ‘up’ ACE2-binding conformation. The combined approach represents an alternative, fast workflow to select binders with neutralizing activity against newly emerging viruses.
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| 10. |
- Karlsson, Elin, et al.
(författare)
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Mapping the transition state for a binding reaction between ancient intrinsically disordered proteins
- 2020
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Ingår i: Journal of Biological Chemistry. - : AMER SOC BIOCHEMISTRY MOLECULAR BIOLOGY INC. - 0021-9258 .- 1083-351X. ; 295:51, s. 17698-17712
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Tidskriftsartikel (refereegranskat)abstract
- Intrinsically disordered protein domains often have multiple binding partners. It is plausible that the strength of pairing with specific partners evolves from an initial low affinity to a higher affinity. However, little is known about the molecular changes in the binding mechanism that would facilitate such a transition. We previously showed that the interaction between two intrinsically disordered domains, NCBD and CID, likely emerged in an ancestral deuterostome organism as a low-affinity interaction that subsequently evolved into a higher-affinity interaction before the radiation of modern vertebrate groups. Here we map native contacts in the transition states of the low-affinity ancestral and high-affinity human NCBD/CID interactions. We show that the coupled binding and folding mechanism is overall similar but with a higher degree of native hydrophobic contact formation in the transition state of the ancestral complex and more heterogeneous transient interactions, including electrostatic pairings, and an increased disorder for the human complex. Adaptation to new binding partners may be facilitated by this ability to exploit multiple alternative transient interactions while retaining the overall binding and folding pathway.
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| 11. |
- Kuehn, Danilo, et al.
(författare)
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Directional sub-femtosecond charge transfer dynamics and the dimensionality of 1T-TaS2
- 2019
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Ingår i: Scientific Reports. - : NATURE PUBLISHING GROUP. - 2045-2322. ; 9
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Tidskriftsartikel (refereegranskat)abstract
- For the layered transition metal dichalcogenide 1T-TaS2, we establish through a unique experimental approach and density functional theory, how ultrafast charge transfer in 1T-TaS2 takes on isotropic three-dimensional character or anisotropic two-dimensional character, depending on the commensurability of the charge density wave phases of 1T-TaS2. The X-ray spectroscopic core-hole-clock method prepares selectively in-and out-of-plane polarized sulfur 3p orbital occupation with respect to the 1T-TaS2 planes and monitors sub-femtosecond wave packet delocalization. Despite being a prototypical two-dimensional material, isotropic three-dimensional charge transfer is found in the commensurate charge density wave phase (CCDW), indicating strong coupling between layers. In contrast, anisotropic two-dimensional charge transfer occurs for the nearly commensurate phase (NCDW). In direct comparison, theory shows that interlayer interaction in the CCDW phase - not layer stacking variations - causes isotropic three-dimensional charge transfer. This is presumably a general mechanism for phase transitions and tailored properties of dichalcogenides with charge density waves.
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| 12. |
- Schröder, Henning, et al.
(författare)
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Varying photo-dissociation mechanisms in Fe(CO)5 and Cr(CO)6 from femtosecond valence photoemission and excited-state moleculardynamics simulations
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- We present measured and calculated time-resolved photoelectron spectra of photoexcited gas-phase Fe(CO)5 and Cr(CO)6. Upon electronic excitation with 266 nm pump pulses and by probing with 23 eV photons from a femtosecond high-order har-monic generation source, we observe differences between Fe(CO)5 and Cr(CO)6 that indicate that the excited-state and dissociation dynamics are slower in Fe(CO)5 than in Cr(CO)6. Changing photoelectron intensities and binding energies combined with excited-state molecular dynamics simulations indicate repopulations of excited states from bound excited to dissociative excited states and to the dissociated species. We find that the more open and flexible structure of Fe(CO)5 with larger metal-carbonyl angles enables the photoexcited states of Fe(CO)5 to dissipate energy by angular distortions as observed in longer populations of bound excited states. The more compactand closed structure of Cr(CO)6 does not enable this relaxation resulting in fasterdissociation.
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| 13. |
- Schulz, Noah, et al.
(författare)
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Surface Termination-Enhanced Magnetism at Nickel Ferrite/2D Nanomaterial Interfaces : Implications for Spintronics
- 2023
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Ingår i: ACS Applied Nano Materials. - : American Chemical Society (ACS). - 2574-0970. ; 6:12, s. 10402-10412
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Tidskriftsartikel (refereegranskat)abstract
- Engineering of interfacial magnetic properties provides an extra edge in designing heterostructures with desired properties for spintronics and spincaloritronics, without drastically changing the structure of the neighboring nonmagnetic material. Here, we report on the surface termination-enhanced magnetic properties of the ferrimagnetic insulator (FMI) nickel ferrite (NFO) with the inclusion of graphene (Gr) and monolayer hexagonal boron nitride (hBN). Depth-dependent X-ray photoelectron spectroscopy (XPS) measurements reveal the presence of a layer of adsorbed oxygen at the NFO/Gr and NFO/hBN interfaces. Magnetometry and transverse susceptibility measurements indicate that the inclusion of monolayer Gr increases the saturation magnetization (Ms) by 40% and decreases the effective magnetic anisotropy by 50% across 5 K ≤ T ≤ 300 K. A similar but less pronounced effect is observed for the inclusion of hBN. Density functional theory calculations further indicate that the increase in MS due to the inclusion of Gr or hBN arises on oxygen-terminated NFO, as observed in XPS measurements. These results present ways for engineering strong interfacial magnetic effects in FMI/2D nanomaterial systems, controlling magnetism by surface termination, and developing advanced spinterfaces for applications in spincaloritronics and spin insulatronics.
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| 14. |
- Sorgenfrei, Felix, et al.
(författare)
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Theory of x-ray absorption spectroscopy for ferrites
- 2024
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Ingår i: Physical Review B. - : American Physical Society. - 2469-9950 .- 2469-9969. ; 109:11
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Tidskriftsartikel (refereegranskat)abstract
- The theoretical calculation of the interaction of electromagnetic radiation with matter remains a challenging problem for contemporary ab initio electronic structure methods, in particular, for x-ray spectroscopies. This is not only due to the strong interaction between the core hole and the photoexcited electron, but also due to the elusive multiplet effects that arise from the Coulomb interaction among the valence electrons. In this work we report a method based on density functional theory in conjunction with multiplet ligand-field theory to investigate various core-level spectroscopies, in particular, x-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD). The developed computational scheme is applied to the L 2 , 3 XAS and XMCD edges of magnetite (Fe 3 O 4 ) as well as cobalt ferrite (CoFe 2 O 4 ) and nickel ferrite (NiFe 2 O 4 ). The results are in overall good agreement with experimental observations, both regarding the XAS L 2 / L 3 branching ratio, the peak positions, as well as the relative intensities. The agreement between theory and experiment is equally good for XAS and the XMCD spectra, for all studied systems. The results are analyzed in terms of e g and t 2 g orbital contribution, and the robustness of the spectra with regard to the uncertainties of the Slater parameters is investigated. The analysis also highlights the strong effect of the 2 p -3 d interaction in x-ray spectroscopy.
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| 15. |
- Sorgenfrei, Nomi L. A. N., et al.
(författare)
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Photodriven Transient Picosecond Top-Layer Semiconductor to Metal Phase-Transition in p-Doped Molybdenum Disulfide
- 2021
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Ingår i: Advanced Materials. - : John Wiley & Sons. - 0935-9648 .- 1521-4095. ; 33:14
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Tidskriftsartikel (refereegranskat)abstract
- Visible light is shown to create a transient metallic S-Mo-S surface layer on bulk semiconducting p-doped indirect-bandgap 2H-MoS2. Optically created electron-hole pairs separate in the surface band bending region of the p-doped semiconducting crystal causing a transient accumulation of electrons in the surface region. This triggers a reversible 2H-semiconductor to 1T-metal phase-transition of the surface layer. Electron-phonon coupling of the indirect-bandgap p-doped 2H-MoS2 enables this efficient pathway even at a low density of excited electrons with a distinct optical excitation threshold and saturation behavior. This mechanism needs to be taken into consideration when describing the surface properties of illuminated p-doped 2H-MoS2. In particular, light-induced increased charge mobility and surface activation can cause and enhance the photocatalytic and photoassisted electrochemical hydrogen evolution reaction of water on 2H-MoS2. Generally, it opens up for a way to control not only the surface of p-doped 2H-MoS2 but also related dichalcogenides and layered systems. The findings are based on the sensitivity of time-resolved electron spectroscopy for chemical analysis with photon-energy-tuneable synchrotron radiation.
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