Thermodynamic assessment of the cesium–oxygen system by coupling density functional theory and CALPHAD approaches

Abstract The thermodynamic properties of cesium oxides were calculated by combining ab initio calculations at 0 K and a quasi-harmonic statistical thermodynamic model to determine the temperature dependency of the thermodynamic properties. In a second approach, the CALPHAD method was used to derive a model describing the Gibbs energy for all the cesium oxide compounds and the liquid phase of the cesium–oxygen system. For this approach, available experimental data in the literature was reviewed and it was concluded that only experimental thermodynamic data for Cs 2 O are reliable. All these data together with the thermodynamic data calculated by combining ab initio and the statistical model were used to assess the Gibbs energy of all the phases of the cesium–oxygen system. A consistent thermodynamic model was obtained. The variation of the relative stability of the different oxides is discussed using structural and bond data for the oxides investigated by ab initio calculations. This work suggests that the melting point for Cs 2 O 2 reported in the literature (863 K) is probably overestimated and should be re-measured.