  We show that the heavy-fermion compound CeCu2Si2 undergoes a transition
between two regimes dominated by different crystal-field states. At low
pressure P and low temperature T the Ce 4f electron resides in the atomic
crystal-field ground state, while at high P or T the electron occupancy and
spectral weight is transferred to an excited crystal-field level that
hybridizes more strongly with itinerant states. These findings result from
first-principles dynamical-mean-field-theory calculations. We predict
experimental signatures of this orbital transition in X-ray spectroscopy. The
corresponding fluctuations may be responsible for the second high-pressure
superconducting dome observed in this and similar materials.
