Role of the defect-core in energetics of vacancies

TL;DR

This study uses electronic structure calculations to reveal that volumetric strains significantly influence vacancy core-energies in aluminum, challenging traditional elastic interaction models and highlighting a universal strain-dependent behavior affecting defect energetics.

Contribution

It demonstrates that vacancy core-energies depend strongly on volumetric strains and introduces a universal curve describing formation energy variations under different macroscopic deformations.

Findings

Vacancy core-energy varies significantly with volumetric strain.

Formation energies of vacancies collapse onto a universal curve.

Volumetric deformation dominates vacancy energetics.

Abstract

Electronic structure calculations at macroscopic scales are employed to investigate the crucial role of a defect-core in the energetics of vacancies in aluminum. We find that vacancy core-energy is significantly influenced by the state of deformation at the vacancy-core, especially volumetric strains. Insights from the core electronic structure and computed displacement fields show that this dependence on volumetric strains is closely related to the changing nature of the core-structure under volumetric deformations. These results are in sharp contrast to mechanics descriptions based on elastic interactions that often consider defect core-energies as an inconsequential constant. Calculations suggest that the variation in core-energies with changing macroscopic deformations is quantitatively more significant than the corresponding variation in relaxation energies associated with elastic fields. Upon studying the influence of various macroscopic deformations, which include volumetric, uniaxial, biaxial and shear deformations, on the formation energies of vacancies, we show that volumetric deformations play a dominant role in governing the energetics of these defects. Further, by plotting formation energies of vacancies and di-vacancies against the volumetric strain corresponding to any macroscopic deformation, we find that all variations in the formation energies collapse on to a universal curve. This suggests a universal role of volumetric strains in the energetics of vacancies. Implications of these results in the context of dynamic failure in metals due to spalling are analyzed.