Cluster Expansion of Electronic Excitations: Application to fcc Ni-Al Alloys

TL;DR

This paper extends the cluster expansion method to electronic excitations in fcc Ni-Al alloys, defining effective cluster density of states (ECDOS) to accurately predict thermodynamic properties and equations of state, especially for disordered systems.

Contribution

It introduces ECDOS as a new approach to model electronic excitations within the cluster expansion framework for alloy thermodynamics.

Findings

ECDOS accurately reproduces DOS and related thermodynamic integrals.

The method is effective for disordered alloys and solid solutions.

Electronic EOS requires considering the full DOS profile, not just constant parameters.

Abstract

The cluster expansion method is applied to electronic excitations and a set of effective cluster density of states (ECDOS) are defined, analogous to effective cluster interactions (ECI). The ECDOS are used to generate alloy thermodynamic properties as well as equation of state (EOS) of electronic excitations for the fcc Ni-Al systems. When parent clusters with small size, the convergence of the expansion is not so good but the electronic density of state (DOS) is well reproduced. However, the integrals of the DOS such as the cluster expanded free energy, entropy and internal energy associated with electronic excitations are well described at the level of the tetrahedron-octahedron cluster approximation, indicating the ECDOS is applicable to produce electronic ECI for cluster variation method or Monte Carlo calculations. On the other hand, the Gruneisen parameter, calculated with first-principles methods, is not any longer a constant and implies that the whole DOS profile should be considered for EOS of electronic excitations, where ECDOS adapts very well for disordered alloys and solid solutions.