Local electronic structure and dynamics of hydrogen in $\text{CeO}_2$

Abstract

The local electronic states of muon (Mu) as an isotope of hydrogen (H) in high-quality single-crystalline ceria (CeO$_2$) are investigated using muon spin rotation/relaxation ($μ\text{SR}$) and first-principles density functional theory (DFT) calculations. Upon positive muon implantation, both paramagnetic (Mu$^0$) and diamagnetic (Mu$^*$) states are observed below $\approx$10 K. Magnetic field dependence of the Mu$^0$ signals combined with DFT results provides evidence for the formation of a polaron state, consisting of Mu bonded to a ligand oxygen and a $4f$ electron localized on a nearby Ce site. The crystal-orientation dependence of the Mu$^0$ signal suggests strong anisotropy of the $4f$ electron due to the spin-orbit coupling with lifted degeneracy. Furthermore, the Mu$^0$ state exhibits transition to the Mu$^*$ state that corresponds to another Mu$^0$ state (exhibiting a diamagnetic response due to fast spin/charge fluctuations) at temperatures above $\approx$10 K, before disappearing above $\approx$30 K. These findings suggest rapid diffusive motion of the $4f$ electrons and/or Mu (as well as H) at higher temperatures.