Theoretical assessment on the possibility of constraining point defect energetics by pseudo-phase transition pressures (1305.6761v1)

Abstract: Making use of the energetics and equations of state of defective uranium dioxide that calculated with first-principles method, we demonstrate a possibility of constraining the formation energy of point defects by measuring the transition pressures of the corresponding pseudo-phase of defects. The mechanically stable range of fluorite structure of UO2, which dictates the maximum possible pressure of relevant pseudo-phase transitions, gives rise to defect formation energies that span a wide band and overlap with the existing experimental estimates. We reveal that the knowledge about pseudo-phase boundaries can not only provide important information of energetics that is helpful for reducing the scattering in current estimates, but also be valuable for guiding theoretical assessments, even to validate or disprove a theory. In order to take defect interactions into account and to extrapolate the physical quantities at finite stoichiometry deviations to that near the stoichiometry, we develop a general formalism to describe the thermodynamics of a defective system. We also show that it is possible to include interactions among defects in a simple expression of point defect model (PDM) by introducing an auxiliary constant mean-field. This generalization of the simple PDM leads to great versatility that allows one to study nonlinear effects of stoichiometry deviation on materials' behavior. It is a powerful tool to extract the defect energetics from finite defect concentrations to the dilute limit. Besides these, the full content of the theoretical formalism and some relevant and interesting issues, including reentrant pseudo-transition, multi-defect coexistence, charged defects, and possible consequence of instantaneous defective response in a quantum crystal, are explored and discussed.