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The dynamics of fragmentation and vibration of molecular systems with a large number of coupled degrees of freedom are key aspects for understanding chemical reactivity and properties. Here we present a resonant inelastic X-ray scattering (RIXS) study to show how it is possible to break down such a complex multidimensional problem into elementary components. Local multimode nuclear wave packets created by X-ray excitation to different core-excited potential energy surfaces (PESs) will act as spatial gates to selectively probe the particular ground-state vibrational modes and, hence, the PES along these modes. We demonstrate this principle by combining ultra-high resolution RIXS measurements for gas-phase water with state-of-the-art simulations.
Selective ultrafast probing of transient hot chemisorbed and precursor States of CO on Ru(0001)
(2013)
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.
Synchrotron radiation facilities routinely operate in a multi-bunch regime, but applications relying on time-of-flight schemes require single bunch operation. Here we show that pulse picking by resonant excitation in a storage ring creates in addition to the multi-bunch operation a distinct and separable single bunch soft X-ray source. It has variable polarization, a photon flux of up to 10(7)-10(9) ph s(-1)/0.1%BW at purity values of 10(4)-10(2) and a repetition rate of 1.25 MHz. The quasi-resonant excitation of incoherent betatron oscillations of electrons allows horizontal pulse separation at variable (also circular) polarization accessible for both, regular 30 ps pulses and ultrashort pulses of 2-3 ps duration. Combined with a new generation of angularly resolving electron spectrometers this creates unique opportunities for time-resolved photoemission studies as confirmed by time-of-flight spectra. Our pulse picking scheme is particularly suited for surface physics at diffraction-limited light sources promising ultimate spectral resolution.
Liquid water molecules interact strongly with each other, forming a fluctuating hydrogen bond network and thereby giving rise to the anomalous phase diagram of liquid water. Consequently, symmetric and asymmetric water molecules have been found in the picosecond time average with IR and optical Raman spectroscopy. With subnatural linewidth resonant inelastic x-ray scattering (RIXS) at vibrational resolution, we take sub-femtosecond snapshots of the electronic and structural properties of water molecules in the hydrogen bond network. We derive a strong dominance of nonsymmetric molecules in liquid water in contrast to the gas phase on the sub-femtosecond timescale of RIXS and determine the fraction of highly asymmetrically distorted molecules.
X-ray absorption spectroscopy at the L-edge of 3d transition metals provides unique information on the local metal charge and spin states by directly probing 3d-derived molecular orbitals through 2p-3d transitions. However, this soft x-ray technique has been rarely used at synchrotron facilities for mechanistic studies of metalloenzymes due to the difficulties of x-ray-induced sample damage and strong background signals from light elements that can dominate the low metal signal. Here, we combine femtosecond soft x-ray pulses from a free-electron laser with a novel x-ray fluorescence-yield spectrometer to overcome these difficulties. We present L-edge absorption spectra of inorganic high-valent Mn complexes (Mn similar to 6-15 mmol/l) with no visible effects of radiation damage. We also present the first L-edge absorption spectra of the oxygen evolving complex (Mn4CaO5) in Photosystem II (Mn < 1 mmol/l) at room temperature, measured under similar conditions. Our approach opens new ways to study metalloenzymes under functional conditions. (C) 2017 Author(s).
Soft X-ray spectroscopy is one of the best tools to directly address the electronic structure, the driving force of chemical reactions. It enables selective studies on sample surfaces to single out reaction centers in heterogeneous catalytic reactions. With core-hole clock methods, specific dynamics are related to the femtosecond life time of a core-hole. Typically, this method is used with photoemission spectroscopy, but advancements in soft X-ray emission techniques render more specific studies possible. With the advent of bright femtosecond pulsed soft X-ray sources, highly selective pump-probe X-ray emission studies are enabled with temporal resolutions down to tens of femtoseconds. This finally allows to study dynamics in the electronic structure of adsorbed reaction centers on the whole range of relevant time scales - closing the gap between kinetic soft X-ray studies and the atto- to femtosecond core-hole clock techniques.
Resonant inelastic soft x-ray scattering (RIXS) spectra excited at the 1 sigma(g) -> 3 sigma(u) resonance in gas-phase O-2 show excitations due to the nuclear degrees of freedom with up to 35 well-resolved discrete vibronic states and a continuum due to the kinetic energy distribution of the separated atoms. The RIXS profile demonstrates spatial quantum beats caused by two interfering wave packets with different momenta as the atoms separate. Thomson scattering strongly affects both the spectral profile and the scattering anisotropy.
As the oldest known magnetic material, magnetite (Fe3O4) has fascinated mankind for millennia. As the first oxide in which a relationship between electrical conductivity and fluctuating/localized electronic order was shown(1), magnetite represents a model system for understanding correlated oxides in general. Nevertheless, the exact mechanism of the insulator-metal, or Verwey, transition has long remained inaccessible(2-8). Recently, three- Fe- site lattice distortions called trimeronswere identified as the characteristic building blocks of the low-temperature insulating electronically ordered phase(9). Here we investigate the Verwey transition with pump- probe X- ray diffraction and optical reflectivity techniques, and show how trimerons become mobile across the insulator-metal transition. We find this to be a two- step process. After an initial 300 fs destruction of individual trimerons, phase separation occurs on a 1.5 +/- 0.2 ps timescale to yield residual insulating and metallic regions. This work establishes the speed limit for switching in future oxide electronics(10).
The electron-phonon scattering is one of the main microscopic mechanisms responsible for the spin-flip in the transient state of ultrafast demagnetization. Here, we present an experimental determination of the temperature-dependent electron-phonon scattering rate in Gd. Using a static x-ray emission spectroscopy method, where the reduction of the decay peak intensities when increasing the temperature is quantified, we measure independently the electron-phonon scattering rate for the 5d and the 4f electrons. We deduce the temperature dependence of scattering for the 5d electrons, while no effect on the phonon population is observed for the 4f electrons. Our results suggest that the ultrafast magnetization dynamics in Gd is triggered by the spin-flip in the 5d electrons. We also evidence the existence of a temperature threshold, above which spin-flip scattering of the 5d electrons takes place. We deduce that during the transient state of ultrafast demagnetization, the exchange energy between 5d electrons has to be overcome before the microscopic electron-phonon scattering process can occur.
Total and partial fluorescence yield (PFY) L-edge x-ray absorption spectra differ from the transmission x-ray absorption spectra (XAS) through state-dependent fluorescence yield across the XAS. For 3d(1) to 3d(9) in octahedral symmetry we apply simulations of PFY and XAS and show how the atomic 2p3d Coulomb exchange parameter G(pd) governs the differences in the L-3/(L-2 + L-3) branching ratio between PFY and XAS. G(pd) orders the XAS final states following Hund's rules creating a strong state-dependent fluorescence decay strength variation across the XAS leading to the differences between PFY and XAS.
Resonant inelastic X-ray scattering and X-ray emission spectroscopy can be used to probe the energy and dispersion of the elementary low-energy excitations that govern functionality in matter: vibronic, charge, spin and orbital excitations(1-7). A key drawback of resonant inelastic X-ray scattering has been the need for high photon densities to compensate for fluorescence yields of less than a per cent for soft X-rays(8). Sample damage from the dominant non-radiative decays thus limits the materials to which such techniques can be applied and the spectral resolution that can be obtained. A means of improving the yield is therefore highly desirable. Here we demonstrate stimulated X-ray emission for crystalline silicon at photon densities that are easily achievable with free-electron lasers(9). The stimulated radiative decay of core excited species at the expense of non-radiative processes reduces sample damage and permits narrow-bandwidth detection in the directed beam of stimulated radiation. We deduce how stimulated X-ray emission can be enhanced by several orders of magnitude to provide, with high yield and reduced sample damage, a superior probe for low-energy excitations and their dispersion in matter. This is the first step to bringing nonlinear X-ray physics in the condensed phase from theory(10-16) to application.
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.
Excited-state proton transfer (ESPT) is a fundamental process in biomolecular photochemistry, but its underlying mediators often evade direct observation. We identify a distinct pathway for ESPT in aqueous 2-thiopyridone, by employing transient N1s X-ray absorption spectroscopy and multi-configurational spectrum simulations. Photoexcitations to the singlet S-2 and S-4 states both relax promptly through intersystem crossing to the triplet T-1 state. The T-1 state, through its rapid population and near nanosecond lifetime, mediates nitrogen site deprotonation by ESPT in a secondary intersystem crossing to the S-0 potential energy surface. This conclusively establishes a dominant ESPT pathway for the system in aqueous solution, which is also compatible with previous measurements in acetonitrile. Thereby, the hitherto open questions of the pathway for ESPT in the compound, including its possible dependence on excitation wavelength and choice of solvent, are resolved.
Tautomerism is one of the most important forms of isomerism, owing to the facile interconversion between species and the large differences in chemical properties introduced by the proton transfer connecting the tautomers. Spectroscopic techniques are often used for the characterization of tautomers. In this context, separating the overlapping spectral response of coexisting tautomers is a long-standing challenge in chemistry. Here, we demonstrate that by using resonant inelastic X-ray scattering tuned to the core excited states at the site of proton exchange between tautomers one is able to experimentally disentangle the manifold of valence excited states of each tautomer in a mixture. The technique is applied to the prototypical keto-enol equilibrium of 3-hydroxypyridine in aqueous solution. We detect transitions from the occupied orbitals into the LUMO for each tautomer in solution, which report on intrinsic and hydrogen-bond-induced orbital polarization within the pi and sigma manifolds at the proton-transfer site.
A scheme for simulations of resonant inelastic X-ray scattering (RIXS) cross-sections within time-dependent density functional theory (TD-DFT) applying the restricted subspace approximation (RSA) is presented. Therein both occupied core and valence Kohn-Sham orbitals are included in the donor-space, while the accepting virtual orbital space in the linear response TD-DFT equations is restricted to efficiently compute both the valence- and core-excited states of the many electron system. This yields a consistent description of all states contributing to the RIXS scattering process within a single calculation. The introduced orbital truncation allows to automatize the method and facilitates RIXS simulations for systems considerably larger than ones accessible with wave-function based methods. Using the nitrogen K-edge RIXS spectra of 2-thiopyridone and its deprotonated anion as a showcase, the method is benchmarked for different exchange-correlation functionals, the impact of the RSA is evaluated, and the effects of explicit solvation are discussed. Improvements compared to simulations in the frozen orbital approximation are also assessed. The general applicability of the framework is further tested by comparison to experimental data from the literature. The use of TD-DFT core-excited states to the calculation of vibrationally resolved RIXS spectra is also investigated by combining potential energy scans along relevant coordinates with wave packet simulations.
Electron-phonon scattering has been studied for silicon carbide (6H-SiC) with resonant inelastic x-ray scattering at the silicon 2p edge. The observed electron-phonon scattering yields a crystal momentum transfer rate per average phonon in 6H-SiC of 1.8 fs(-1) while it is 0.2 fs(-1) in crystalline silicon. The angular momentum transfer rate per average phonon for 6H-SiC is 0.1 fs(-1), which is much higher than 0.0035 fs(-1) obtained for crystalline silicon in a previous study. The higher electron-phonon scattering rates in 6H-SiC are a result of the larger electron localization at the silicon atoms in 6H-SiC as compared to crystalline silicon. While delocalized valence electrons can screen effectively (part of) the electron-phonon interaction, this effect is suppressed for 6H-SiC in comparison to crystalline silicon. Smaller contributions to the difference in electron-phonon scattering rates between 6H-SiC and silicon arise from the lower atomic mass of carbon versus silicon and the difference in local symmetry.
At BESSY II a confocal plane grating spectrometer for resonant inelastic X-ray scattering (RIXS) is currently under commissioning. The new endstation operates with a source size of 4 x 1 mu m(2) provided by its dedicated beamline. The RIXS-spectrometer covers an energy range from 50 eV to 1000 eV, providing a resolving power E/Delta E of 5000-15,000. The beamline allows full polarization control and gives a photon flux of up to 7 x 10(14) photons/s/0.1 A/0.1%bandwidth by offering a resolving power E/Delta E of 4000-12,000.
Auger-photoelectron coincidence spectroscopy (APECS) has been used to examine the electron correlation and itinerance effects in transition metals Cu, Ni and Co.
It is shown that the LVV Auger, in coincidence with 2p photoelectrons, spectra can be represented using atomic multiplet positions if the 3d-shell is localized (atomic-like) and with a self-convoluted valence band for band-like (itinerant) materials as explained using the Cini-Sawatzky model.
For transition metals, the 3d band changes from band-like to localized with increasing atomic number, with the possibility of a mixed behavior.
Our result shows that the LVV spectra of Cu can be represented by atomic multiplet calculations, those of Co resemble the self-convolution of the valence band and those of Ni are a mixture of both, consistent with the Cini-Sawatzky model.
Pump-probe photoelectron spectroscopy (PES) is a versatile tool to investigate the dynamics of transient states of excited matter. Vacuum space-charge effects can mask these dynamics and complicate the interpretation of electron spectra. Here we report on space-charge effects in Au 4f photoemission from a polycrystalline gold surface, excited with moderately intense 90 ps (FWHM) soft x-ray probe pulses, under the influence of the Coulomb forces exerted by a pump electron cloud, which was produced by intense 40 fs laser pulses. The experimentally observed kinetic energy shift and spectral broadening of the Au 4f lines, measured with highly-efficient time-of-flight spectroscopy, are in good agreement with simulations utilizing a mean-field model of the electrostatic pump electron potential. This confirms that the line broadening is predominantly caused by variations in the take-off time of the probe electrons without appreciable influence of local scattering events. Our findings might be of general interest for pump-probe PES with picosecond-pulse-length sources.
Understanding and controlling properties of transition metal complexes is a crucial step towards tailoring materials for sustainable energy applications. In a systematic approach, we use resonant inelastic X-ray scattering to study the influence of ligand substitution on the valence electronic structure around an aqueous iron(II) center. Exchanging cyanide with 2-2′-bipyridine ligands reshapes frontier orbitals in a way that reduces metal 3d charge delocalization onto the ligands. This net decrease of metal–ligand covalency results in lower metal-centered excited state energies in agreement with previously reported excited state dynamics. Furthermore, traces of solvent-effects were found indicating a varying interaction strength of the solvent with ligands of different character. Our results demonstrate how ligand exchange can be exploited to shape frontier orbitals of transition metal complexes in solution-phase chemistry; insights upon which future efforts can built when tailoring the functionality of photoactive systems for light-harvesting applications.
The central moiety of porphyrins is shown to control the charge state of the inner complex and links it by covalent interaction to the peripheral substituents. This link, which enables the versatile functions of porphyrins, is not picked up in the established, reduced four orbital picture [Gouterman, J. Mol. Spectrosc., 1961, 6, 138]. X-ray absorption spectroscopy at the N K-edge with density functional theory approaches gives access to the full electronic structure, in particular the pi* manifold beyond the Gouterman orbitals. Systematic variation of the central moiety highlights two linked, governing trends: The ionicity of the porphyrin center increases from the aminic N-H to N-Cu to N-Zn to N-Mg to the iminic N:. At the same time covalency with peripheral substituents increases and compensates the buildup of high charge density at the coordinated nitrogen sites.
Thermal evolution of the band edges of 6H-SiC: X-ray methods compared to the optical band gap
(2014)
The band gap of semiconductors like silicon and silicon carbide (SIC) is the key for their device properties. In this research, the band gap of 6H-SiC and its temperature dependence were analyzed with silicon 2p X-ray absorption spectroscopy (XAS), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS) allowing for a separate analysis of the conduction-band minimum (CBM) and valence-band maximum (VBM) components of the band gap. The temperature-dependent asymmetric band gap shrinking of 6H-SiC was determined with a valence-band slope of +2.45 x 10(-4) eV/K and a conduction-band slope of -1.334 x 10(-4) eV/K. The apparent asymmetry, e.g., that two thirds of the band-gap shrinking with increasing temperature is due to the VBM evolution in 6H-SiC, is similar to the asymmetry obtained for pure silicon before. The overall band gap temperature-dependence determined with XAS and nonresonant XES is compared to temperature-dependent optical studies. The core-excitonic binding energy appearing in the Si 2p XAS is extracted as the main difference. In addition, the energy loss of the onset of the first band in RIXS yields to values similar to the optical band gap over the tested temperature range. (C) 2014 Elsevier B.V. All rights reserved.
How different microscopic mechanisms of ultrafast spin dynamics coexist and interplay is not only relevant for the development of spintronics but also for the thorough description of physical systems out-of-equilibrium. In pure crystalline ferromagnets, one of the main microscopic mechanism of spin relaxation is the electron-phonon (el-ph) driven spin-flip, or Elliott-Yafet, scattering. Unexpectedly, recent experiments with ferro- and ferrimagnetic alloys have shown different dynamics for the different sublattices. These distinct sublattice dynamics are contradictory to the Elliott-Yafet scenario. In order to rationalize this discrepancy, it has been proposed that the intra- and intersublattice exchange interaction energies must be considered in the microscopic demagnetization mechanism, too. Here, using a temperature-dependent x-ray emission spectroscopy (XES) method, we address experimentally the element specific el-ph angular momentum transfer rates, responsible for the spin-flips in the respective (sub)lattices of Fe20Ni80, Fe50Ni50 and pure nickel single crystals. We establish how the deduced rate evolution with the temperature is linked to the exchange coupling constants reported for different alloy stoichiometries and how sublattice exchange energies threshold the related el-ph spin-flip channels. Thus, these results evidence that the Elliott-Yafet spin-flip scattering, thresholded by sublattice exchange energies, is the relevant microscopic process to describe sublattice dynamics in alloys and elemental magnetic systems.
Dynamics in materials typically involve different degrees of freedom, like charge, lattice, orbital and spin in a complex interplay. Time-resolved resonant inelastic X-ray scattering (RIXS) as a highly selective tool can provide unique insight and follow the details of dynamical processes while resolving symmetries, chemical and charge states, momenta, spin configurations, etc. In this paper, we review examples where the intrinsic scattering duration time is used to study femtosecond phenomena. Free-electron lasers access timescales starting in the sub-ps range through pump-probe methods and synchrotrons study the time scales longer than tens of ps. In these examples, time-resolved resonant inelastic X-ray scattering is applied to solids as well as molecular systems.
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.
Resonant soft x-ray diffraction (RSXD) with femtosecond (fs) time resolution is a powerful tool for disentangling the interplay between different degrees of freedom in strongly correlated electron materials. It allows addressing the coupling of particular degrees of freedom upon an external selective perturbation, e. g., by an optical or infrared laser pulse. Here, we report a time-resolved RSXD experiment from the prototypical correlated electron material magnetite using soft x-ray pulses from the free-electron laser FLASH in Hamburg. We observe ultrafast melting of the charge-orbital order leading to the formation of a transient phase, which has not been observed in equilibrium.
We present a setup combining a liquid flatjet sample delivery and a MHz laser system for time-resolved soft X-ray absorption measurements of liquid samples at the high brilliance undulator beamline UE52-SGM at Bessy II yielding unprecedented statistics in this spectral range. We demonstrate that the efficient detection of transient absorption changes in transmission mode enables the identification of photoexcited species in dilute samples. With iron(II)-trisbipyridine in aqueous solution as a benchmark system, we present absorption measurements at various edges in the soft X-ray regime. In combination with the wavelength tunability of the laser system, the set-up opens up opportunities to study the photochemistry of many systems at low concentrations, relevant to materials sciences, chemistry, and biology.
We present a setup combining a liquid flatjet sample delivery and a MHz laser system for time-resolved soft X-ray absorption measurements of liquid samples at the high brilliance undulator beamline UE52-SGM at Bessy II yielding unprecedented statistics in this spectral range. We demonstrate that the efficient detection of transient absorption changes in transmission mode enables the identification of photoexcited species in dilute samples. With iron(II)-trisbipyridine in aqueous solution as a benchmark system, we present absorption measurements at various edges in the soft X-ray regime. In combination with the wavelength tunability of the laser system, the set-up opens up opportunities to study the photochemistry of many systems at low concentrations, relevant to materials sciences, chemistry, and biology. (C) 2017 Author(s).
Modern stationary X-ray spectroscopy is unable to resolve rotational structure.
In the present paper, we propose to use time-resolved two color X-ray pump-probe spectroscopy with picosecond resolution for real-time monitoring of the rotational dynamics induced by the recoil effect.
The proposed technique consists of two steps.
The first short pump X-ray pulse ionizes the valence electron, which transfers angular momentum to the molecule.
The second time-delayed short probe X-ray pulse resonantly excites a 1s electron to the created valence hole.
Due to the recoil-induced angular momentum the molecule rotates and changes the orientation of transition dipole moment of core-excitation with respect to the transition dipole moment of the valence ionization, which results in a temporal modulation of the probe X-ray absorption as a function of the delay time between the pulses.
We developed an accurate theory of the X-ray pump-probe spectroscopy of the recoil-induced rotation and study how the energy of the photoelectron and thermal dephasing affect the structure of the time-dependent X-ray absorption using the CO molecule as a case-study.
We also discuss the feasibility of experimental observation of our theoretical findings, opening new perspectives in studies of molecular rotational dynamics.
Ultrafast and Energy-Efficient Quenching of Spin Order: Antiferromagnetism Beats Ferromagnetism
(2017)
By comparing femtosecond laser pulse induced ferro- and antiferromagnetic dynamics in one and the same material-metallic dysprosium-we show both to behave fundamentally different. Antiferromagnetic order is considerably faster and much more efficiently reduced by optical excitation than its ferromagnetic counterpart. We assign the fast and extremely efficient process in the antiferromagnet to an interatomic transfer of angular momentum within the spin system. Our findings imply that this angular momentum transfer channel is effective in other magnetic metals with nonparallel spin alignment. They also point out a possible route towards energy-efficient spin manipulation for magnetic devices.
In this combined theoretical and experimental study we report on an analysis of the resonant inelastic X-ray scattering (RIXS) spectra of gas phase water via the lowest dissociative core-excited state |1s−1O4a11〉. We focus on the spectral feature near the dissociation limit of the electronic ground state. We show that the narrow atomic-like peak consists of the overlapping contribution from the RIXS channels back to the ground state and to the first valence excited state |1b−114a11〉 of the molecule. The spectral feature has signatures of ultrafast dissociation (UFD) in the core-excited state, as we show by means of ab initio calculations and time-dependent nuclear wave packet simulations. We show that the electronically elastic RIXS channel gives substantial contribution to the atomic-like resonance due to the strong bond length dependence of the magnitude and orientation of the transition dipole moment. By studying the RIXS for an excitation energy scan over the core-excited state resonance, we can understand and single out the molecular and atomic-like contributions in the decay to the lowest valence-excited state. Our study is complemented by a theoretical discussion of RIXS in the case of isotopically substituted water (HDO and D2O) where the nuclear dynamics is significantly affected by the heavier fragments' mass.
The femtosecond excited-state dynamics following resonant photoexcitation enable the selective deformation of N-H and N-C chemical bonds in 2-thiopyridone in aqueous solution with optical or X-ray pulses. In combination with multiconfigurational quantum-chemical calculations, the orbital-specific electronic structure and its ultrafast dynamics accessed with resonant inelastic X-ray scattering at the N 1s level using synchrotron radiation and the soft X-ray free-electron laser LCLS provide direct evidence for this controlled photoinduced molecular deformation and its ultrashort time-scale.
The femtosecond excited-state dynamics following resonant photoexcitation enable the selective deformation of N-H and N-C chemical bonds in 2-thiopyridone in aqueous solution with optical or X-ray pulses. In combination with multiconfigurational quantum-chemical calculations, the orbital-specific electronic structure and its ultrafast dynamics accessed with resonant inelastic X-ray scattering at the N 1s level using synchrotron radiation and the soft X-ray free-electron laser LCLS provide direct evidence for this controlled photoinduced molecular deformation and its ultrashort time-scale.
Ultrafast soft X-ray emission spectroscopy of surface adsorbates using an X-ray free electron laser
(2013)
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.
Irradiating a ferromagnet with a femtosecond laser pulse is known to induce an ultrafast demagnetization within a few hundred femtoseconds. Here we demonstrate that direct laser irradiation is in fact not essential for ultrafast demagnetization, and that electron cascades caused by hot electron currents accomplish it very efficiently. We optically excite a Au/Ni layered structure in which the 30 nm Au capping layer absorbs the incident laser pump pulse and subsequently use the X-ray magnetic circular dichroism technique to probe the femtosecond demagnetization of the adjacent 15 nm Ni layer. A demagnetization effect corresponding to the scenario in which the laser directly excites the Ni film is observed, but with a slight temporal delay. We explain this unexpected observation by means of the demagnetizing effect of a superdiffusive current of non-equilibrium, non-spin-polarized electrons generated in the Au layer.
Die Femtosekundendynamik nach resonanten Photoanregungen mit optischen und Röntgenpulsen ermöglicht eine selektive Verformung von chemischen N‐H‐ und N‐C‐Bindungen in 2‐Thiopyridon in wässriger Lösung. Die Untersuchung der orbitalspezifischen elektronischen Struktur und ihrer Dynamik auf ultrakurzen Zeitskalen mit resonanter inelastischer Röntgenstreuung an der N1s‐Resonanz am Synchrotron und dem Freie‐Elektronen‐Laser LCLS in Kombination mit quantenchemischen Multikonfigurationsberechnungen erbringen den direkten Nachweis dieser kontrollierten photoinduzierten Molekülverformungen und ihrer ultrakurzen Zeitskala.
Die Femtosekundendynamik nach resonanten Photoanregungen mit optischen und Röntgenpulsen ermöglicht eine selektive Verformung von chemischen N‐H‐ und N‐C‐Bindungen in 2‐Thiopyridon in wässriger Lösung. Die Untersuchung der orbitalspezifischen elektronischen Struktur und ihrer Dynamik auf ultrakurzen Zeitskalen mit resonanter inelastischer Röntgenstreuung an der N1s‐Resonanz am Synchrotron und dem Freie‐Elektronen‐Laser LCLS in Kombination mit quantenchemischen Multikonfigurationsberechnungen erbringen den direkten Nachweis dieser kontrollierten photoinduzierten Molekülverformungen und ihrer ultrakurzen Zeitskala.
Amorphous materials represent a large and important emerging area of material's science. Amorphous oxides are key technological oxides in applications such as a gate dielectric in Complementary metal-oxide semiconductor devices and in Silicon-Oxide-Nitride-Oxide-Silicon and TANOS (TaN-Al2O3-Si3N4-SiO2-Silicon) flash memories. These technologies are required for the high packing density of today's integrated circuits. Therefore the investigation of defect states in these structures is crucial. In this work we present X-ray synchrotron measurements, with an energy resolution which is about 5-10 times higher than is attainable with standard spectrometers, of amorphous alumina. We demonstrate that our experimental results are in agreement with calculated spectra of amorphous alumina which we have generated by stochastic quenching. This first principles method, which we have recently developed, is found to be superior to molecular dynamics in simulating the rapid gas to solid transition that takes place as this material is deposited for thin film applications. We detect and analyze in detail states in the band gap that originate from oxygen pairs. Similar states were previously found in amorphous alumina by other spectroscopic methods and were assigned to oxygen vacancies claimed to act mutually as electron and hole traps. The oxygen pairs which we probe in this work act as hole traps only and will influence the information retention in electronic devices. In amorphous silica oxygen pairs have already been found, thus they may be a feature which is characteristic also of other amorphous metal oxides.
Uppsala and Berkeley
(2022)
The development of modern photoelectron spectroscopy is reviewed with a special focus on the importance of research at Uppsala University and at Berkeley. The influence of two pioneers, Kai Siegbahn and Dave Shirley, is underlined. Early interaction between the two centers helped to kick-start the field. Both laboratories have continued to play an important role in the field, both in terms of creating new experimental capabilities and developing the theoretical understanding of the spectroscopic processes.
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. (C) 2015 Author(s).
The valence orbitals of aqueous histidine under basic, neutral and acidic conditions and their X-ray induced transformations have been monitored through N 1s resonant inelastic X-ray scattering. Using density functional ab initio molecular dynamics simulations in the core-hole state within the Z + 1 approximation, core-excitation-induced molecular transformations are quantified. Spectroscopic evidence for a highly directional X-ray-induced local N-H dissociation within the scattering duration is presented for acidic histidine. Our report demonstrates a protonation-state and chemical-environment dependent propensity for a molecular dissociation, which is induced by the absorption of high energy photons. This case study indicates that structural deformations in biomolecules under exposure to ionizing radiation, yielding possible alteration or loss of function, is highly dependent on the physiological state of the molecule upon irradiation.
We present an X-ray-optical cross-correlator for the soft (> 150 eV) up to the hard X-ray regime based on a molybdenum-silicon superlattice. The cross-correlation is done by probing intensity and position changes of superlattice Bragg peaks caused by photoexcitation of coherent phonons. This approach is applicable for a wide range of X-ray photon energies as well as for a broad range of excitation wavelengths and requires no external fields or changes of temperature. Moreover, the cross-correlator can be employed on a 10 ps or 100 fs time scale featuring up to 50% total X-ray reflectivity and transient signal changes of more than 20%. (C) 2016 Author(s).
We present an X-ray-optical cross-correlator for the soft (> 150 eV) up to the hard X-ray regime based on a molybdenum-silicon superlattice. The cross-correlation is done by probing intensity and position changes of superlattice Bragg peaks caused by photoexcitation of coherent phonons. This approach is applicable for a wide range of X-ray photon energies as well as for a broad range of excitation wavelengths and requires no external fields or changes of temperature. Moreover, the cross-correlator can be employed on a 10 ps or 100 fs time scale featuring up to 50% total X-ray reflectivity and transient signal changes of more than 20%. (C) 2016 Author(s).
The valence-excited states of ferric and ferrous hexacyanide ions in aqueous solution were mapped by resonant inelastic X-ray scattering (RIXS) at the Fe L-2,L-3 and N K edges. Probing of both the central Fe and the ligand N atoms enabled identification of the metal-and ligand-centered excited states, as well as ligand-to-metal and metal-to-ligand charge-transfer excited states. Ab initio calculations utilizing the RASPT2 method were used to simulate the Fe L-2,L-3-edge RIXS spectra and enabled quantification of the covalencies of both occupied and empty orbitals of pi and sigma symmetry. We found that pi back-donation in the ferric complex is smaller than that in the ferrous complex. This is evidenced by the relative amounts of Fe 3d character in the nominally 2 pi CN- molecular orbital of 7% and 9% in ferric and ferrous hexacyanide, respectively. Utilizing the direct sensitivity of Fe L-3-edge RIXS to the Fe 3d character in the occupied molecular orbitals, we also found that the donation interactions are dominated by sigma bonding. The latter was found to be stronger in the ferric complex, with an Fe 3d contribution to the nominally 5 sigma CN- molecular orbitals of 29% compared to 20% in the ferrous complex. These results are consistent with the notion that a higher charge at the central metal atom increases donation and decreases back-donation.
X-ray free electron lasers (XFELs) enable unprecedented new ways to study the electronic structure and dynamics of transition metal systems. L-edge absorption spectroscopy is a powerful technique for such studies and the feasibility of this method at XFELs for solutions and solids has been demonstrated. However, the required x-ray bandwidth is an order of magnitude narrower than that of self-amplified spontaneous emission (SASE), and additional monochromatization is needed. Here we compare L-edge x-ray absorption spectroscopy (XAS) of a prototypical transition metal system based on monochromatizing the SASE radiation of the linac coherent light source (LCLS) with a new technique based on self-seeding of LCLS. We demonstrate how L-edge XAS can be performed using the self-seeding scheme without the need of an additional beam line monochromator. We show how the spectral shape and pulse energy depend on the undulator setup and how this affects the x-ray spectroscopy measurements. (C) 2016 Optical Society of America
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. (C) 2015 AIP Publishing LLC.
The active ions in typical laser crystals were studied with Resonant Inelastic X-ray Scattering (RIXS) and Partial Fluorescence Yield X-ray Absorption (PFY-XAS) spectroscopies as solid state model systems for dilute active centers. We analyzed Ti3+ and Cr3+ in alpha-Al2O3:Ti3+ and LiCaAlF6:Cr3+, respectively. The comparison of experimental data with semi-empirical multiplet calculations provides insights into the electronic structure and shows how measured crystal field energies are related across different spectroscopies.