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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.
Transition-metal complexes have long attracted interest for fundamental chemical reactivity studies and possible use in solar energy conversion(1,2). Electronic excitation, ligand loss from the metal centre, or a combination of both, creates changes in charge and spin density at the metal site(3-11) that need to be controlled to optimize complexes for photocatalytic hydrogen production(8) and selective carbon-hydrogen bond activation(9-11). 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) in solution, that the photo-induced removal of CO generates the 16-electron Fe(CO)(4) species, a homogeneous catalyst(12,13) with an electron deficiency at the Fe centre(14,15), 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, 16-20), 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.
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.
Picosecond x-ray pulses are extracted with a phase-locked x-ray pulse selector at 1.25 MHz repetition rate from the pulse trains of the accelerator-driven multiuser x-ray source BESSY II preserving the peak brilliance at high pulse purity. The system consists of a specially designed in-vacuum chopper wheel rotating with approximate to 1 kHz angular frequency. The wheel is driven in an ultrahigh vacuum and is levitated on magnetic bearings being capable of withstanding high centrifugal forces. Pulses are picked by 1252 high-precision slits of 70 mu m width on the outer rim of the wheel corresponding to a temporal opening window of the chopper of 70 ns. We demonstrate how the electronic phase stabilization of +/- 2 ns together with an arrival time jitter of the individual slits of the same order of magnitude allows us to pick short single bunch x-ray pulses out of a 200 ns ion clearing gap in a multibunch pulse train as emitted from a synchrotron facility at 1.25 MHz repetition rate with a pulse purity below the shot noise detection limit. The approach is applicable to any high-repetition pulsed radiation source, in particular in the x-ray spectral range up to 10 keV. The opening window in a real x-ray beamline, its stability, as well as the limits of mechanical pulse picking techniques in the MHz range are discussed. (C) 2015 Optical Society of America
A soft X-ray approach to electron-phonon interactions beyond the Born-Oppenheimer approximation
(2011)
With modern soft X-ray methods, the whole field of electron-phonon interactions becomes accessible directly in the ultrafast time domain with ultrashort pulsed X-ray sources, as well as in the energy domain through modern highly resolving spectrometers. The well-known core-hole clock approach plays an intermediate role, resolving energetic and temporal features at the same time. In this perspective paper, we review several experiments to illustrate the modern advances in the selective study of electron-phonon interactions as fundamentally determining ingredients for materials properties. We present the different complementary approaches that can be taken with soft X-ray methods to conquer this field beyond the Born-Oppenheimer approximation.
The unprecedented beam properties of free-electron laser based X-ray sources enable novel resonant inelastic X-ray scattering (RIXS) experiments. Femtosecond time-resolved RIXS can be used to follow charge, spin and structural dynamics of dilute solute molecules in solution. Ultrashort X-ray pulses allow probing of highly radiation sensitive states of matter such as the metastable phase of supercooled liquid water. Nonlinear X-ray probes like amplified spontaneous emission and stimulated resonant X-ray scattering provide an enhanced selectivity and sensitivity as well as a path to control radiation damage and increase the photon yields in RIXS experiments. (C) 2015 Elsevier B.V. All rights reserved.
Determining covalent and charge-transfer contributions to bonding in solution has remained an experimental challenge. Here, the quenching of fluorescence decay channels as expressed in dips in the L-edge X-ray spectra of solvated 3d transition-metal ions and complexes was reported as a probe. With a full set of experimental and theoretical ab initio L-edge X-ray spectra of aqueous Cr3+, including resonant inelastic X-ray scattering, we address covalency and charge transfer for this prototypical transition-metal ion in solution. We dissect local atomic effects from intermolecular interactions and quantify X-ray optical effects. We find no evidence for the asserted ultrafast charge transfer to the solvent and show that the dips are readily explained by X-ray optical effects and local atomic state dependence of the fluorescence yield. Instead, we find, besides ionic interactions, a covalent contribution to the bonding in the aqueous complex of ligand-to-metal charge-transfer character.
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.
The combination of a non-coated silicon photodiode with electron repelling meshes makes a versatile detector for total fluorescence yield and electron yield techniques highly suitable for x-ray absorption spectroscopy. In particular, a copper mesh with a bias voltage allows to suppress or transmit the electron yield signal. The performance of this detection scheme has been characterized by near edge x-ray absorption fine structure studies of thermal oxidized silicon and sapphire. The results show that the new detector probes both electron yield and for a bias voltage exceeding the maximum photon energy the total fluorescence yield.