The electronic structure and thermodynamic properties of $\mathrm{Ce}{\mathrm{O}}_{2}$ and ${\mathrm{Ce}}_{2}{\mathrm{O}}_{3}$ have been studied from first principles by the all-electron projector-augmented-wave (PAW) method, as implemented in the ab initio total-energy and molecular-dynamics program VASP (Vienna ab initio simulation package). The local density approximation $(\mathrm{LDA})+U$ formalism has been used to account for the strong on-site Coulomb repulsion among the localized Ce $4f$ electrons. We discuss how the properties of $\mathrm{Ce}{\mathrm{O}}_{2}$ and ${\mathrm{Ce}}_{2}{\mathrm{O}}_{3}$ are affected by the choice of $U$ as well as the choice of exchange-correlation potential, i.e., the local density approximation or the generalized gradient approximation. Further, reduction of $\mathrm{Ce}{\mathrm{O}}_{2}$, leading to formation of ${\mathrm{Ce}}_{2}{\mathrm{O}}_{3}$ and $\mathrm{Ce}{\mathrm{O}}_{2\ensuremath{-}x}$, and its dependence on $U$ and exchange-correlation potential have been studied in detail. Our results show that by choosing an appropriate $U$ it is possible to consistently describe structural, thermodynamic, and electronic properties of $\mathrm{Ce}{\mathrm{O}}_{2}$, ${\mathrm{Ce}}_{2}{\mathrm{O}}_{3}$, and $\mathrm{Ce}{\mathrm{O}}_{2\ensuremath{-}x}$, which enables modeling of redox processes involving ceria-based materials.

Modeling of<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mrow><mml:mi mathvariant="normal">Ce</mml:mi><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn>2</mml:mn></mml:msub></mml:mrow></mml:math>,<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="normal">Ce</mml:mi><mml:mn>2</mml:mn></mml:msub><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn>3</mml:mn></mml:msub></mml:mrow></mml:math...

Modeling ofCeO2,Ce2O3</mml:math...