133 research outputs found
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Ultrafast Coherent Control and Characterization of Surface Reactions using FELs
The microscopic understanding of reactions at surfaces requires an in-depth knowledge of the dynamics of elementary processes on an ultrafast timescale. This can be accomplished using an ultrafast excitation to initiate a chemical reaction and then probe the progression of the reaction with an ultrashort x-ray pulse from the FEL. There is a great potential to use atom-specific spectroscopy involving core levels to probe the chemical nature, structure and bonding of species on surfaces. The ultrashort electron pulse obtained in the linear accelerator to feed the X-ray FEL can also be used for generation of coherent synchrotron radiation in the low energy THz regime to be used as a pump. This radiation has an energy close to the thermal excitations of low-energy vibrational modes of molecules on surfaces and phonons in substrates. The coherent THz radiation will be an electric field pulse with a certain direction that can collectively manipulate atoms or molecules on surfaces. In this respect a chemical reaction can be initiated by collective atomic motion along a specific reaction coordinate. If the coherent THz radiation is generated from the same source as the X-ray FEL radiation, full-time synchronization for pump-probe experiments will be possible. The combination of THz and X-ray spectroscopy could be a unique opportunity for FEL facilities to conduct ultrafast chemistry studies at surfaces
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Electronic structure effects in liquid water studied by photoelectron spectroscopy and density functional theory
We present valence photoelectron emission spectra of liquid water in comparison with gas-phase water, ice close to the melting point, low temperature amorphous and crystalline ice. All aggregation states have major electronic structure changes relative to the free molecule, with rehybridization and development of bonding and anti-bonding states accompanying the hydrogen bond formation. Sensitivity to the local structural order, most prominent in the shape and splitting of the occupied 3a{sub 1} orbital, is understood from the electronic structure averaging over various geometrical structures, and reflects the local nature of the orbital interaction
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Autocatalytic water dissociation on Cu(110) at near ambient conditions
Autocatalytic dissociation of water on the Cu(110) metal surface is demonstrated based on X-ray photoelectron spectroscopy studies carried out in-situ under near ambient conditions of water vapor pressure (1 Torr) and temperature (275-520 K). The autocatalytic reaction is explained as the result of the strong hydrogen-bond in the H{sub 2}O-OH complex of the dissociated final state, which lowers the water dissociation barrier according to the Broensted-Evans-Polanyi relations. A simple chemical bonding picture is presented which predicts autocatalytic water dissociation to be a general phenomenon on metal surfaces
Ultrafast adsorbate excitation probed with sub-ps resolution XAS
We use a pump-probe scheme to measure the time evolution of the C K-edge
X-ray absorption spectrum (XAS) from CO/Ru(0001) after excitation by an
ultrashort high-intensity optical laser pulse. Due to the short duration of the
X-ray probe pulse and precise control of the pulse delay, the
excitation-induced dynamics during the first ps after the pump can be resolved
with unprecedented time resolution. By comparing with theoretical (DFT)
spectrum calculations we find high excitation of the internal stretch and
frustrated rotation modes occurring within 200 fs of laser excitation, as well
as thermalization of the system in the ps regime. The ~100 fs initial
excitation of these CO vibrational modes is not readily rationalized by
traditional theories of nonadiabatic coupling of adsorbates to metal surfaces,
e. g. electronic frictions based on first order electron-phonon coupling or
transient population of adsorbate resonances. We suggest that coupling of the
adsorbate to non-thermalized electron-hole pairs is responsible for the
ultrafast initial excitation of the modes.Comment: 16 pages, 16 figures. To be published in Physical Review Letters:
https://journals.aps.org/prl/accepted/c1070Y74M8b18063d9cd0221b000631d50ef7a24
Ultrafast Adsorbate Excitation Probed with Subpicosecond-Resolution X-Ray Absorption Spectroscopy
We use a pump-probe scheme to measure the time evolution of the C K-edge x-ray absorption spectrum from CO/Ru(0001) after excitation by an ultrashort high-intensity optical laser pulse. Because of the short duration of the x-ray probe pulse and precise control of the pulse delay, the excitation-induced dynamics during the first picosecond after the pump can be resolved with unprecedented time resolution. By comparing with density functional theory spectrum calculations, we find high excitation of the internal stretch and frustrated rotation modes occurring within 200 fs of laser excitation, as well as thermalization of the system in the picosecond regime. The ∼100 fs initial excitation of these CO vibrational modes is not readily rationalized by traditional theories of nonadiabatic coupling of adsorbates to metal surfaces, e.g., electronic frictions based on first order electron-phonon coupling or transient population of adsorbate resonances. We suggest that coupling of the adsorbate to nonthermalized electron-hole pairs is responsible for the ultrafast initial excitation of the modes
Atom-Specific Probing of Electron Dynamics in an Atomic Adsorbate by Time-Resolved X-Ray Spectroscopy
The electronic excitation occurring on adsorbates at ultrafast timescales from optical lasers that initiate surface chemical reactions is still an open question. Here, we report the ultrafast temporal evolution of x-ray absorption spectroscopy (XAS) and x-ray emission spectroscopy (XES) of a simple well-known adsorbate prototype system, namely carbon (C) atoms adsorbed on a nickel [Ni(100)] surface, following intense laser optical pumping at 400 nm. We observe ultrafast (∼100 fs) changes in both XAS and XES showing clear signatures of the formation of a hot electron-hole pair distribution on the adsorbate. This is followed by slower changes on a few picoseconds timescale, shown to be consistent with thermalization of the complete C/Ni system. Density functional theory spectrum simulations support this interpretation
Atom-Specific Probing of Electron Dynamics in an Atomic Adsorbate by Time-Resolved X-ray Spectroscopy
The electronic excitation occurring on adsorbates at ultrafast time scales
from optical lasers that initiate surface chemical reactions is still an open
question. Here, we report the ultrafast temporal evolution of X-ray absorption
spectroscopy (XAS) and X-ray emission spectroscopy (XES) of a simple well known
adsorbate prototype system, namely carbon (C) atoms adsorbed on a nickel
(Ni(100)) surface, following intense laser optical pumping at 400 nm. We
observe ultrafast (~100 fs) changes in both XAS and XES showing clear
signatures of the formation of a hot electron-hole pair distribution on the
adsorbate. This is followed by slower changes on a few ps time scale, shown to
be consistent with thermalization of the complete C/Ni system. Density
functional theory spectrum simulations support this interpretation.Comment: 33 pages, 12 figures. Submitted to Physical Review Letter
Symmetry-Resolved CO Desorption and Oxidation Dynamics on O/Ru(0001) Probed at the C K-edge by Ultrafast X-Ray Spectroscopy
We report on carbon monoxide desorption and oxidation induced by 400 nm femtosecond laser excitation on the O/Ru(0001) surface probed by time-resolved x-ray absorption spectroscopy (TR-XAS) at the carbon K-edge. The experiments were performed under constant background pressures of CO (6 × 10−8 Torr) and O2 (3 × 10−8 Torr). Under these conditions, we detect two transient CO species with narrow 2π* peaks, suggesting little 2π* interaction with the surface. Based on polarization measurements, we find that these two species have opposing orientations: (1) CO favoring a more perpendicular orientation and (2) CO favoring a more parallel orientation with respect to the surface. We also directly detect gas-phase CO2 using a mass spectrometer and observe weak signatures of bent adsorbed CO2 at slightly higher x-ray energies than the 2π* region. These results are compared to previously reported TR-XAS results at the O K-edge, where the CO background pressure was three times lower (2 × 10−8 Torr) while maintaining the same O2 pressure. At the lower CO pressure, in the CO 2π* region, we observed adsorbed CO and a distribution of OC–O bond lengths close to the CO oxidation transition state, with little indication of gas-like CO. The shift toward “gas-like” CO species may be explained by the higher CO exposure, which blocks O adsorption, decreasing O coverage and increasing CO coverage. These effects decrease the CO desorption barrier through dipole–dipole interaction while simultaneously increasing the CO oxidation barrier
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