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Modeling the Elastic Energy of Alloys: Potential Pitfalls of Continuum Treatments

Some issues that arise when modeling elastic energy for binary alloys are discussed within the context of a Keating model and density functional calculations. The Keating model is based on atomistic modeling of elastic interactions in binary alloy using harmonic springs with species dependent equilibrium lengths. It is demonstrated that the continuum limit for the strain field are the usual equations of linear elasticity for alloys and that they correctly capture the coarse-grained displacement field. In addition, it is established that Euler-Lagrange equation of the continuum limit of the elastic energy will yield the same strain field equation. However, a direct calculation of the elastic energy of the atomistic model reveals that the continuum expression for the elastic energy is both qualitatively and quantitatively incorrect. This is because it does not take atomistic scale compositional non-uniformity into account. Importantly, we also shows that finely mixed alloys tend to have more elastic energy than segregated systems, which is the opposite of predictions by some continuum theories. It is also shown that for strained thin films the traditionally used effective misfit for alloys systematically underestimate the strain energy. In some models, this drawback is handled by including an elastic contribution to the enthalpy of mixing which is characterized in terms of the continuum concentration. The direct calculation of the atomistic model reveals that this approach suffers serious difficulties. It is demonstrated that elastic contribution to the enthalpy of mixing is non-isotropic and scale dependent. It also shown that such effects are present in density-functional theory calculations for the Si/Ge and Ag/Pt systems. This work demonstrates that it is critical to include the microscopic arrangements in any elastic model to achieve even qualitatively correct behavior.