The isotropic magnetic moment of a free atom is shown to develop giant magnetic anisotropy energy due to symmetry reduction at an atomically ordered surface. Single cobalt atoms deposited onto platinum (111) are found to have a magnetic anisotropy energy of 9 millielectron volts per atom arising from the combination of unquenched orbital moments (1.1 Bohr magnetons) and strong spin-orbit coupling induced by the platinum substrate. By assembling cobalt nanoparticles containing up to 40 atoms, the magnetic anisotropy energy is further shown to be dependent on single-atom coordination changes. These results confirm theoretical predictions and are of fundamental value to understanding how magnetic anisotropy develops in finite-sized magnetic particles.

X-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD) have been used to study transition metal impurities on K and Na films. The multiplet structure of the XAS spectra indicates that Fe, Co, and Ni have localized atomic ground states with predominantly $d^7$, $d^8$, and $d^9$ character, respectively. XMCD shows that the localized impurity states possess large, atomiclike, magnetic orbital moments that are progressively quenched as clusters are formed. Ni impurities on Na films are found to be nonmagnetic, with a strongly increased $d^{10}$ character of the impurity state. The results show that the high magnetic moments of transition metals in alkali hosts originate from electron localization.

We exploit time- and angle-resolved photoemission spectroscopy to determine the evolution of the out-of-equilibrium electronic structure of the topological insulator Bi2Se3. The response of the Fermi-Dirac distribution to ultrashort IR laser pulses has been studied by modeling the dynamics of hot electrons after optical excitation. We disentangle a large increase in the effective temperature (T*) from a shift of the chemical potential ($\mu${}*), which is consequence of the ultrafast photodoping of the conduction band. The relaxation dynamics of T* and $\mu${}* are k independent and these two quantities uniquely define the evolution of the excited charge population. We observe that the energy dependence of the nonequilibrium charge population is solely determined by the analytical form of the effective Fermi-Dirac distribution.

The two single-pass, externally seeded free-electron lasers (FELs) of the FERMI user facility are designed around Apple-II-type undulators that can operate at arbitrary polarization in the vacuum ultraviolet-to-soft x-ray spectral range. Furthermore, within each FEL tuning range, any output wavelength and polarization can be set in less than a minute of routine operations. We report the first demonstration of the full output polarization capabilities of FERMI FEL-1 in a campaign of experiments where the wavelength and nominal polarization are set to a series of representative values, and the polarization of the emitted intense pulses is thoroughly characterized by three independent instruments and methods, expressly developed for the task. The measured radiation polarization is consistently $>90\%$ and is not significantly spoiled by the transport optics; differing, relative transport losses for horizontal and vertical polarization become more prominent at longer wavelengths and lead to a non-negligible ellipticity for an originally circularly polarized state. The results from the different polarimeter setups validate each other, allow a cross-calibration of the instruments, and constitute a benchmark for user experiments.

The first steps in photochemical processes, such as photosynthesis or animal vision, involve changes in electronic and geometric structure on extremely short time scales. Time-resolved photoelectron spectroscopy is a natural way to measure such changes, but has been hindered hitherto by limitations of available pulsed light sources in the vacuum-ultraviolet and soft X-ray spectral region, which have insufficient resolution in time and energy simultaneously. The unique combination of intensity, energy resolution, and femtosecond pulse duration of the FERMI-seeded free-electron laser can now provide exceptionally detailed information on photoexcitation–deexcitation and fragmentation in pump-probe experiments on the 50-femtosecond time scale. For the prototypical system acetylacetone we report here electron spectra measured as a function of time delay with enough spectral and time resolution to follow several photoexcited species through well-characterized individual steps, interpreted using state-of-the-art static and dynamics calculations. These results open the way for investigations of photochemical processes in unprecedented detail.