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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.
The simultaneous detection of energy, momentum and temporal information in electron spectroscopy is the key aspect to enhance the detection efficiency in order to broaden the range of scientific applications. Employing a novel 60 degrees wide angle acceptance lens system, based on an additional accelerating electron optical element, leads to a significant enhancement in transmission over the previously employed 30 degrees electron lenses. Due to the performance gain, optimized capabilities for time resolved electron spectroscopy and other high transmission applications with pulsed ionizing radiation have been obtained. The energy resolution and transmission have been determined experimentally utilizing BESSY II as a photon source. Four different and complementary lens modes have been characterized. (C) 2017 The Authors. Published by Elsevier B.V.
We analyze the effects of covalent interactions in Ni 2p3d resonant inelastic X-ray scattering (RIXS) spectra from aqueous Ni2+ ions and find that the relative RIXS intensities of ligand-to-metal charge-transfer final states with respect to the ligand-field final states reflect the covalent mixing between Ni 3d and water orbitals. Specifically, the experimental intensity ratio at the Ni L-3-edge allows to determine that the Ni 3d orbitals have on average 5.5% of water character. We propose that 2p3d RIXS at the Ni L-3-edge can be utilized to quantify covalency in Ni complexes without the use of external references or simulations.
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.
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.
The simultaneous detection of energy, momentum and temporal information in electron spectroscopy is the key aspect to enhance the detection efficiency in order to broaden the range of scientific applications. Employing a novel 60 degrees wide angle acceptance lens system, based on an additional accelerating electron optical element, leads to a significant enhancement in transmission over the previously employed 30 degrees electron lenses. Due to the performance gain, optimized capabilities for time resolved electron spectroscopy and other high transmission applications with pulsed ionizing radiation have been obtained. The energy resolution and transmission have been determined experimentally utilizing BESSY II as a photon source. Four different and complementary lens modes have been characterized. (C) 2017 The Authors. Published by Elsevier B.V.
A new energy and angular electron analyzer ArTOF (Angular Resolved Time of Flight) is described. The analyzer is based on simultaneous measurement of flight times and angles in an advanced electron lens system. In angular modes the new analyzer combines an increase in transmission by almost three orders of magnitude with improved resolution, in comparison to standard state-of-the-art electron spectrometers. In this report we describe some design principles and we give a review of calibration and alignment procedures necessary for the use of the ArTOF on a synchrotron radiation facility. Our program scripts to handle the large datasets are also discussed. Furthermore we give a broad description of the new research fields that benefit from the use of the ArTOF and give a short summary of the first results of angle resolved photoemission measurement with ArTOF using the single-bunch X-ray pulses from the BESSY II storage ring facility. (C) 2013 Published by Elsevier B.V.
Bonding of the Ni2+(aq) complex is investigated with an unprecedented combination of resonant inelastic X-ray scattering (RIXS) measurements and ab initio calculations at the Ni L absorption edge. The spectra directly reflect the relative energies of the ligand-field and charge-transfer valence-excited states. They give element-specific access with atomic resolution to the ground-state electronic structure of the complex and allow quantification of ligand-field strength and 3d-3d electron correlation interactions in the Ni2+(aq) complex. The experimentally determined ligand-field strength is 10Dq = 1.1 eV. This and the Racah parameters characterizing 3d-3d Coulomb interactions B = 0.13 eV and C = 0.42 eV as readily derived from the measured energies match very well with the results from UV-vis spectroscopy. Our results demonstrate how L-edge RIXS can be used to complement existing spectroscopic tools for the investigation of bonding in 3d transition-metal coordination compounds in solution. The ab initio RASPT2 calculation is successfully used to simulate the L-edge RIXS spectra.
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.