Femtosecond Spin-State Switching Dynamics of Fe(II) Complexes Condensed in Thin Films.

The tailoring of spin-crossover films has made significant progress over the past decade, mostly motivated by the prospect in technological applications. In contrast to spin-crossover complexes in solution, the investigation of the ultrafast switching in spin-crossover films has remained scarce. Combining the progress in molecule synthesis and film growth with the opportunities at X-ray free-electron lasers, we study the photoinduced spin-state switching dynamics of a molecular film at room temperature.

Femtosecond Electron-Transfer Dynamics across the DO/Cs/Cu(111) Interface: The Impact of Hydrogen Bonding.

Hydrogen bonding is essential in electron-transfer processes at water-electrode interfaces. We study the impact of the H-bonding of water as a solvent molecule on real-time electron-transfer dynamics across a Cs-Cu(111) ion-metal interface using femtosecond time-resolved two-photon photoelectron spectroscopy. We distinguish in the formed water-alkali aggregates two regimes below and above two water molecules per ion.

Electron population dynamics in resonant non-linear x-ray absorption in nickel at a free-electron laser.

Free-electron lasers provide bright, ultrashort, and monochromatic x-ray pulses, enabling novel spectroscopic measurements not only with femtosecond temporal resolution: The high fluence of their x-ray pulses can also easily enter the regime of the non-linear x-ray-matter interaction. Entering this regime necessitates a rigorous analysis and reliable prediction of the relevant non-linear processes for future experiment designs. Here, we show non-linear changes in the -edge absorption of metallic nickel thin films, measured with fluences up to 60 J/cm.

Hydration at Highly Crowded Interfaces.

Understanding the molecular and electronic structure of solvated ions at surfaces requires an analysis of the interactions between the surface, the ions, and the solvent environment on equal footing. Here, we tackle this challenge by exploring the initial stages of Cs^{+} hydration on a Cu(111) surface by combining experiment and theory. Remarkably, we observe "inside-out" solvation of Cs^{+} ions, i.

Photon-shot-noise-limited transient absorption soft X-ray spectroscopy at the European XFEL.

Femtosecond transient soft X-ray absorption spectroscopy (XAS) is a very promising technique that can be employed at X-ray free-electron lasers (FELs) to investigate out-of-equilibrium dynamics for material and energy research. Here, a dedicated setup for soft X-rays available at the Spectroscopy and Coherent Scattering (SCS) instrument at the European X-ray Free-Electron Laser (European XFEL) is presented. It consists of a beam-splitting off-axis zone plate (BOZ) used in transmission to create three copies of the incoming beam, which are used to measure the transmitted intensity through the excited and unexcited sample, as well as to monitor the incoming intensity.

Impact of Electron Solvation on Ice Structures at the Molecular Scale.

Electron attachment and solvation at ice structures are well-known phenomena. The energy liberated in such events is commonly understood to cause temporary changes at such ice structures, but it may also trigger permanent modifications to a yet unknown extent. We determine the impact of electron solvation on DO structures adsorbed on Cu(111) with low-temperature scanning tunneling microscopy, two-photon photoemission, and ab initio theory.

Microscopic Insight into Electron-Induced Dissociation of Aromatic Molecules on Ice.

We use scanning tunneling microscopy, photoelectron spectroscopy, and ab initio calculations to investigate the electron-induced dissociation of halogenated benzene molecules adsorbed on ice. Dissociation of halobenzene is triggered by delocalized excess electrons attaching to the π^{*} orbitals of the halobenzenes from where they are transferred to σ^{*} orbitals. The latter orbitals provide a dissociative potential surface.

Nonequilibrium electron and lattice dynamics of strongly correlated BiSrCaCuO single crystals.

The interplay between the electronic and lattice degrees of freedom in nonequilibrium states of strongly correlated systems has been debated for decades. Although progress has been made in establishing a hierarchy of electronic interactions with the use of time-resolved techniques, the role of the phonons often remains in dispute, a situation highlighting the need for tools that directly probe the lattice. We present the first combined megaelectron volt ultrafast electron diffraction and time- and angle-resolved photoemission spectroscopy study of optimally doped BiSrCaCuO.

Femtosecond Spin Current Pulses Generated by the Nonthermal Spin-Dependent Seebeck Effect and Interacting with Ferromagnets in Spin Valves.

Using the sensitivity of optical second harmonic generation to currents, we demonstrate the generation of 250-fs long spin current pulses in Fe/Au/Fe/MgO(001) spin valves. The temporal profile of these pulses indicates ballistic transport of hot electrons across a sub-100 nm Au layer. The pulse duration is primarily determined by the thermalization time of laser-excited hot carriers in Fe.

Nanoscale interface confinement of ultrafast spin transfer torque driving non-uniform spin dynamics.

Spintronics had a widespread impact over the past decades due to transferring information by spin rather than electric currents. Its further development requires miniaturization and reduction of characteristic timescales of spin dynamics combining the sub-nanometre spatial and femtosecond temporal ranges. These demands shift the focus of interest towards the fundamental open question of the interaction of femtosecond spin current (SC) pulses with a ferromagnet (FM).

Ultrafast electron dynamics at water covered alkali adatoms adsorbed on Cu(111).

Here we report on the ultrafast electron dynamics of the alkalis Na, K, and Cs coadsorbed with D2O on Cu(111) surfaces, which we investigated with femtosecond time-resolved two-photon photoemission. The well known transient electronic binding energy stabilization in bare adsorbed alkalis is enhanced by the presence of water which acts as a solvent and increases the transient energy gain. We observe for all adsorbed alkalis a transient binding energy stabilization of 100-300 meV.

FemtoSpeX: a versatile optical pump-soft X-ray probe facility with 100 fs X-ray pulses of variable polarization.

Here the major upgrades of the femtoslicing facility at BESSY II (Khan et al., 2006) are reviewed, giving a tutorial on how elliptical-polarized ultrashort soft X-ray pulses from electron storage rings are generated at high repetition rates. Employing a 6 kHz femtosecond-laser system consisting of two amplifiers that are seeded by one Ti:Sa oscillator, the total average flux of photons of 100 fs duration (FWHM) has been increased by a factor of 120 to up to 10(6) photons s(-1) (0.

Ultrafast transport of laser-excited spin-polarized carriers in Au/Fe/MgO(001).

Hot carrier-induced spin dynamics is analyzed in epitaxial Au/Fe/MgO(001) by a time domain approach. We excite a spin current pulse in Fe by 35 fs laser pulses. The transient spin polarization, which is probed at the Au surface by optical second harmonic generation, changes its sign after a few hundred femtoseconds.

Hot-electron-driven enhancement of spin-lattice coupling in Gd and Tb 4f ferromagnets observed by femtosecond x-ray magnetic circular dichroism.

Femtosecond x-ray magnetic circular dichroism was used to study the time-dependent magnetic moment of 4f electrons in the ferromagnets Gd and Tb, which are known for their different spin-lattice coupling. We observe a two-step demagnetization with an ultrafast demagnetization time of 750 fs identical for both systems and slower times which differ sizeably with 40 ps for Gd and 8 ps for Tb. We conclude that spin-lattice coupling in the electronically excited state is enhanced up to 50 times compared to equilibrium.

Reactivity of water-electron complexes on crystalline ice surfaces.

The interactions between long-living electrons trapped in defects of crystalline D2O and electronegative molecules have been investigated using two-photon photoemission spectroscopy. When covered by a Xe adlayer, the spectroscopic signature of the trapped electrons vanishes, which provides evidence that the trapping sites are located on the surface of the crystalline ice. The reactive character of these surface-trapped electrons with molecules has been studied.

A surface science approach to ultrafast electron transfer and solvation dynamics at interfaces.

Excess electrons in polar media, such as water or ice, are screened by reorientation of the surrounding molecular dipoles. This process of electron solvation is of vital importance for various fields of physical chemistry and biology as, for instance, in electrochemistry or photosynthesis. Generation of such excess electrons in bulk water involves either photoionization of solvent molecules or doping with e.

Determination of the electron's solvation site on D2O/Cu(111) using Xe overlayers and femtosecond photoelectron spectroscopy.

We investigate the binding site of solvated electrons in amorphous D(2)O clusters and D(2)O wetting layers adsorbed on Cu(111) by means of two-photon photoelectron (2PPE) spectroscopy. On the basis of different interactions of bulk- or surface-bound solvated electrons with rare gas atoms, titration experiments using Xe overlayers reveal the location of the electron solvation sites. In the case of flat clusters with a height of 2-4 bilayers adsorbed on Cu(111), solvated electrons are found to reside at the ice-vacuum interface, whereas a bulk character is found for solvated electrons in wetting layers.

Ultrafast electron transfer dynamics at NH3/Cu(111) interfaces: determination of the transient tunneling barrier.

Electron transfer (ET) dynamics at molecule-metal interfaces plays a key role in various fields as surface photochemistry or the development of molecular electronic devices. The bare transfer process is often described in terms of tunneling through an interfacial barrier that depends on the distance of the excited electron to the metal substrate. However, a quantitative characterization of such potential barriers is still lacking.

Ultrafast electron dynamics at ice-metal interfaces: competition between heterogeneous electron transfer and solvation.

Microscopic insight into heterogeneous electron transfer requires an understanding of the participating donor and acceptor states and of their respective interaction. In the regime of strong electronic coupling, two limits have been discussed where either the states overlap directly or the states are separated by a potential barrier. In both situations, the transfer probability is determined by the magnitude of the wave function overlap, whereby in the case of the potential barrier, its width and height are rate limiting.