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The determination of depth profiles across interfaces is of primary importance in many scientific and technological areas. Photoemission spectroscopy is in principle well suited for this purpose, yet a quantitative implementation for investigations of liquid-vapor interfaces is hindered by the lack of understanding of electron-scattering processes in liquids. Previous studies have shown, however, that core-level photoelectron angular distributions (PADs) are altered by depth-dependent elastic electron scattering and can, thus, reveal information on the depth distribution of species across the interface. Here, we explore this concept further and show that the anisotropy parameter characterizing the PAD scales linearly with the average distance of atoms along the surface normal. This behavior can be accounted for in the low-collision-number regime. We also show that results for different atomic species can be compared on the same length scale. We demonstrate that atoms separated by about 1~\AA~along the surface normal can be clearly distinguished with this method, achieving excellent depth resolution., Comment: Submitted to Phys. Rev. Lett

The possibility of suddenly ionized molecules undergoing extremely fast electron hole dynamics prior to significant structural change was first recognized more than 20 years ago and termed charge migration. The accurate probing of ultrafast electron hole dynamics requires measurements that have both sufficient temporal resolution and can detect the localization of a specific hole within the molecule. We report an investigation of the dynamics of inner valence hole states in isopropanol where we use an x-ray pump/x-ray probe experiment, with site and state-specific probing of a transient hole state localized near the oxygen atom in the molecule, together with an ab initio theoretical treatment. We record the signature of transient hole dynamics and make the first observation of dynamics driven by frustrated Auger-Meitner transitions. We verify that the hole lifetime is consistent with our theoretical prediction. This state-specific measurement paves the way to widespread application for observations of transient hole dynamics localized in space and time in molecules and thus to charge transfer phenomena that are fundamental in chemical and material physics.

Intense X-ray free-electron lasers (XFELs) can rapidly excite matter, leaving it in inherently unstable states that decay on femtosecond timescales. As the relaxation occurs primarily via Auger emission, excited state observations are constrained by Auger decay. In situ measurement of this process is therefore crucial, yet it has thus far remained elusive at XFELs due to inherent timing and phase jitter, which can be orders of magnitude larger than the timescale of Auger decay. Here, we develop a new approach termed self-referenced attosecond streaking, based upon simultaneous measurements of streaked photo- and Auger electrons. Our technique enables sub-femtosecond resolution in spite of jitter. We exploit this method to make the first XFEL time-domain measurement of the Auger decay lifetime in atomic neon, and, by using a fully quantum-mechanical description, retrieve a lifetime of $2.2^{ + 0.2}_{ - 0.3}$ fs for the KLL decay channel. Importantly, our technique can be generalised to permit the extension of attosecond time-resolved experiments to all current and future FEL facilities., Comment: Main text: 20 pages, 3 figures. Supplementary information: 17 pages, 6 figures

Relative cross sections for the valence shell photoionisation (PI) of $\rm ^2S$ ground level and $\rm ^2D$ metastable Ca$^{+}$ ions were measured with high energy resolution by using the ion-photon merged-beams technique at the Advanced Light Source. Overview measurements were performed with a full width at half maximum bandpass of $\Delta E =17$~meV, covering the energy range 20~eV -- 56~eV. Details of the PI spectrum were investigated at energy resolutions reaching the level of $\Delta E=3.3$~meV. The photon energy scale was calibrated with an uncertainty of $\pm5$~meV. By comparison with previous absolute measurements %by Kjeldsen et al in the energy range 28~eV -- 30.5~eV and by Lyon et al in the energy range 28~eV -- 43~eV the present experimental high-resolution data were normalised to an absolute cross-section scale and the fraction of metastable Ca$^{+}$ ions that were present in the parent ion beam was determined to be 18$\pm$4\%. Large-scale R-matrix calculations using the Dirac Coulomb approximation and employing 594 levels in the close-coupling expansion were performed for the Ca$^{+}(3s^23p^64s~^2\textrm{S}_{1/2})$ and Ca$^{+}(3s^2 3p^6 3d~^2\textrm{D}_{3/2,5/2})$ levels. The experimental data are compared with the results of these calculations and previous theoretical and experimental studies., Comment: 19 pages, 14 figures, 3 tables

Arbitrary manipulation of the temporal and spectral properties of X-ray pulses at free-electron lasers (FELs) would revolutionize many experimental applications. At the Linac Coherent Light Source at Stanford National Accelerator Laboratory, the momentum phase-space of the FEL driving electron bunch can be tuned to emit a pair of X-ray pulses with independently variable photon energy and femtosecond delay. However, while accelerator parameters can easily be adjusted to tune the electron bunch phase-space, the final impact of these actuators on the X-ray pulse cannot be predicted with sufficient precision. Furthermore, shot-to-shot instabilities that distort the pulse shape unpredictably cannot be fully suppressed. Therefore, the ability to directly characterize the X-rays is essential to ensure precise and consistent control. In this work, we have generated X-ray pulse pairs and characterized them on a single-shot basis with femtosecond resolution through time-resolved photoelectron streaking spectroscopy. This achievement completes an important step toward future X-ray pulse shaping techniques.

This paper gives an account of our progress towards performing femtosecond time-resolved photoelectron diffraction on gas-phase molecules in a pump-probe setup combining optical lasers and an X-ray Free-Electron Laser. We present results of two experiments aimed at measuring photoelectron angular distributions of laser-aligned 1-ethynyl-4-fluorobenzene (C8H5F) and dissociating, laseraligned 1,4-dibromobenzene (C6H4Br2) molecules and discuss them in the larger context of photoelectron diffraction on gas-phase molecules. We also show how the strong nanosecond laser pulse used for adiabatically laser-aligning the molecules influences the measured electron and ion spectra and angular distributions, and discuss how this may affect the outcome of future time-resolved photoelectron diffraction experiments., Comment: 24 pages, 10 figures, Faraday Discussions 171

We investigate the creation of double K-shell holes in N2 molecules via sequential absorption of two photons on a timescale shorter than the core-hole lifetime by using intense x-ray pulses from the Linac Coherent Light Source free electron laser. The production and decay of these states is characterized by photoelectron spectroscopy and Auger electron spectroscopy. In molecules, two types of double core holes are expected, the first with two core holes on the same N atom, and the second with one core hole on each N atom. We report the first direct observations of the former type of core hole in a molecule, in good agreement with theory, and provide an experimental upper bound for the relative contribution of the latter type., Comment: 5 pages, 3 figures

We present a new method for ultrafast spectroscopy of molecular photoexcited dynamics. The technique uses a pair of femtosecond pulses: a photoexcitation pulse initiating excited state dynamics followed by a soft x-ray (SXR) probe pulse that core ionizes certain atoms inside the molecule. We observe the Auger decay of the core hole as a function of delay between the photoexcitation and SXR pulses. The core hole decay is particularly sensitive to the local valence electrons near the core and shows new types of propensity rules, compared to dipole selection rules in SXR absorption or emission spectroscopy. We apply the delayed ultrafast x-ray Auger probing (DUXAP) method to the specific problem of nucleobase photoprotection to demonstrate its potential. The ultraviolet photoexcited \pi\pi* states of nucleobases are prone to chemical reactions with neighboring bases. To avoid this, the single molecules funnel the \pi\pi* population to lower lying electronic states on an ultrafast timescale under violation of the Born-Oppenheimer approximation. The new type of propensity rule, which is confirmed by Auger decay simulations, allows us to have increased sensitivity on the direct relaxation from the \pi\pi* state to the vibrationally hot electronic ground state. For the nucleobase thymine, we measure a decay constant of 300 fs in agreement with previous quantum chemical simulations.

We have performed X-ray two-photon photoelectron spectroscopy (XTPPS) using the Linac Coherent Light Source (LCLS) X-ray free-electron laser (FEL) in order to study double core-hole (DCH) states of CO2, N2O and N2. The experiment verifies the theory behind the chemical sensitivity of two-site (ts) DCH states by comparing a set of small molecules with respect to the energy shift of the tsDCH state and by extracting the relevant parameters from this shift., Comment: 11 pages, 2 figures

We present the results of an experiment where amorphous carbon was irradiated by femtosecond x-ray free electron laser pulses. The 830 eV laser pulses induce a phase transition in the material which is characterized ex-situ. The phase transition energy threshold is determined by measuring the surface of each irradiated area using an optical Nomarski microscope. The threshold fluence is found to be 282 +/- 11 mJ/cm^2, corresponding to an absorbed dose at the surface of 131 +/-5 meV/atom. Atomic force microscopy measurements show volume expansion of the irradiated sample area, suggesting a solid to solid phase transition. Deeper insight into the phase transition is gained by using scanning photoelectron microscopy and micro-Raman spectroscopy. Photoelectron microscopy shows graphitization, i.e. modification from sp3 to sp2 hybridization, of the irradiated material. The micro-Raman spectra show the appearance of local order, i.e. formation of graphite nanocrystals. Finally, the nature of the phase transition is discussed, taking into account previous theory and experimental results.