Interconnection of defect entropies and enthalpies in BaF$_2$ revisited

TL;DR

This study confirms a thermodynamical model predicting a proportional relationship between defect entropies and enthalpies in BaF2, based on ab-initio calculations and bulk elastic data, across multiple defect processes.

Contribution

It provides the first comprehensive validation of the defect entropy-enthalpy proportionality in BaF2 using ab-initio calculations and elastic data.

Findings

Proportionality between defect entropies and enthalpies in BaF2.

Bulk elasticity and expansivity govern defect thermodynamics.

Validation of the thermodynamical model for defect parameters.

Abstract

Here, we investigate the following key prediction of a thermodynamical model that interrelates the defect parameters with the bulk elastic and expansivity data: for various defect processes in a given matrix material, a proportionality exists between defect entropies and enthalpies. The investigation is focused on BaF2 for which ab-initio calculations within density functional theory and the generalized-gradient approximation have been recently made as far as the formation and migration of intrinsic defects is concerned, as well as for the elastic constants. Four defect processes have been studied in BaF$_2$: Anion Frenkel formation, fluorine vacancy migration, fluorine interstitial motion and electrical relaxation associated with a single tetravalent uranium. For these processes, the entropies and enthalpies vary by almost two orders of magnitude and reveal a proportionality between them. We find that this proportionality is solely governed by the bulk elasticity and expansivity data, which conforms to the aforementioned thermodynamical model.