Ultrafast electronic processes in an insulator The Be and O sites in BeO

The short time dynamics of amorphous beryllium oxide a BeO has been investigated for electronic excitation ionization by fast incident electrons, as well as by Ar7 , Ar15 , Xe15 , and Xe31 ions at velocities of 6 10 the speed of light. Site specific Auger electron spectra induced by fast heavy ions are the central point of this investigation. Electron induced Auger spectra serve as a reference and electron energy loss EELS spectroscopy as well as resonant inelastic X ray scattering RIXS are invoked for quantitative understanding. For the heavy ion case, we observe strong variations in the corresponding spectral distributions of Be K and O K Auger lines. These are related to local changes of the electron density, of the electron temperature and even of the electronic band structure of BeO on a femtosecond time scale after the passage of highly charged heavy ions

Towards time resolved core level photoelectron spectroscopy with femtosecond x-ray free-electron lasers

We have performed core level photoelectron spectroscopy on a W(110) single crystal with femtosecond XUV pulses from the free-electron laser at Hamburg (FLASH). We demonstrate experimentally and through theoretical modelling that for a suitable range of photon fluences per pulse, time-resolved photoemission experiments on solid surfaces are possible. Using FLASH pulses in combination with a synchronized optical laser, we have performed femtosecond time-resolved core-level photoelectron spectroscopy and observed sideband formation on the W 4f lines indicating a cross correlation between femtosecond optical and XUV pulses. © IOP Publishing Ltd and Deutsche Physikalische Gesellschaft

Resonant Auger spectroscopy at the L2,3 shake-up thresholds as a probe of electron correlation effects in nickel

The excitation energy dependence of the three-hole satellites in the L3-M4,5M4,5 and L2-M4,5M4,5 Auger spectra of nickel metal has been measured using synchrotron radiation. The satellite behavior in the non-radiative emission spectra at the L3 and L2 thresholds is compared and the influence of the Coster-Kronig channel explored. The three-hole satellite intensity at the L3 Auger emission line reveals a peak structure at 5 eV above the L3 threshold attributed to resonant processes at the 2p53d9 shake-up threshold. This is discussed in connection with the 6-eV feature in the x-ray absorption spectrum.Comment: 8 pages, 4 figures; http://prb.aps.org/abstract/PRB/v58/i7/p3677_

Time resolved study of recoil induced rotation by X ray pump X ray probe spectroscopy

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 dynamic

Strong Influence of Coadsorbate Interaction on CO Desorption Dynamics on Ru(0001) Probed by Ultrafast X-Ray Spectroscopy and \u3cem\u3eAb Initio\u3c/em\u3e Simulations

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 5σ 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

Selective ultrafast probing of transient hot chemisorbed and precursor states of CO on Ru(0001)

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

One dimensional cuts through multidimensional potential energy surfaces by tunable x rays

The concept of the potential energy surface PES and directional reaction coordinates is the backbone of our description of chemical reaction mechanisms. Although the eigenenergies of the nuclear Hamiltonian uniquely link a PES to its spectrum, this information is in general experimentally inaccessible in large polyatomic systems. This is due to near degenerate rovibrational levels across the parameter space of all degrees of freedom, which effectively forms a pseudospectrum given by the centers of gravity of groups of close lying vibrational levels. We show here that resonant inelastic x ray scattering RIXS constitutes an ideal probe for revealing one dimensional cuts through the ground state PES of molecular systems, even far away from the equilibrium geometry, where the independent mode picture is broken. We strictly link the center of gravity of close lying vibrational peaks in RIXS to a pseudospectrum which is shown to coincide with the eigenvalues of an effective one dimensional Hamiltonian along the propagation coordinate of the core excited wave packet. This concept, combined with directional and site selectivity of the core excited states, allows us to experimentally extract cuts through the ground state PES along three complementary directions for the showcase H2O molecul