A change of orbital state alters the coupling between ions and their surroundings drastically. Orbital excitations are hence key to understand and control interaction of ions. Rare-earth elements with strong magneto-crystalline anisotropy (MCA) are important ingredients for magnetic devices. Thus, control of their localized 4f magnetic moments and anisotropy is one major challenge in ultrafast spin physics. With time-resolved x-ray absorption and resonant inelastic scattering experiments, we show for Tb metal that 4f-electronic excitations out of the ground-state multiplet occur after optical pumping. These excitations are driven by inelastic 5d-4f-electron scattering, altering the 4f-orbital state and consequently the MCA with important implications for magnetization dynamics in 4f-metals and more general for the excitation of localized electronic states in correlated materials.

Charles University Faculty of Mathematics and Physics DCMP 12116 Prague 2 Czech Republic

Department of Condensed Matter Physics Faculty of Mathematics and Physics Charles University CZ 121 16 Prague Czech Republic

Deutsches Elektronen Synchrotron DESY Notkestraße 85 22607 Hamburg Germany

Elettra Sincrotrone Trieste S C p A Strada statale 14 km 163 5 34149 Basovizza Trieste Italy

European XFEL Holzkoppel 4 22869 Schenefeld Germany

Freie Universität Berlin Fachbereich Physik Arnimallee 14 14195 Berlin Germany

Helmholtz Zentrum Berlin für Materialien und Energie GmbH Albert Einstein Str 15 12489 Berlin Germany

Instituto de Ciencia de Materiales de Madrid CSIC Cantoblanco 28049 Madrid Spain

Sorbonne Université CNRS Laboratoire de Chimie Physique Matière et Rayonnement 75005 Paris France

Universität Hamburg Physics Department Luruper Chaussee 149 22761 Hamburg Germany

Uppsala University Department of Physics and Astronomy P O Box 516 75120 Uppsala Sweden

VSB Technical University Ostrava IT4Innovations 708 00 Ostrava Czech Republic

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