Efficient determination of alloy ground-state structures

TL;DR

This paper introduces an efficient method to identify alloy ground-state structures using convex hulls and cluster expansion, validated by DFT calculations on various alloys and complex oxides.

Contribution

It presents a novel approach combining convex hulls and cluster expansion to rapidly find ground states without initial energy information.

Findings

Successfully identified ground-state structures for multiple alloys.

Validated the method with DFT calculations showing accurate formation energies.

Extended the approach to complex oxides like MgAl2O4 spinel.

Abstract

We propose an efficient approach to accurately finding the ground-state structures in alloys based on the cluster expansion method. In this approach, a small number of candidate ground-state structures are obtained without any information of the energy. To generate the candidates, we employ the convex hull constructed from the correlation functions of all possible structures by using an efficient algorithm. This approach is applicable to not only simple lattices but also complex lattices. Firstly, we evaluate the convex hulls for binary alloys with four types of simple lattice. Then we discuss the structures on the vertices. To examine the accuracy of this approach, we perform a set of density functional theory calculations and the cluster expansion for Ag-Au alloy and compare the formation energies of the vertex structures with those of all possible structures. As applications, the ground-state structures of the intermetallic compounds CuAu, CuAg, CuPd, AuAg, AuPd, AgPd, MoTa, MoW and TaW are similarly evaluated. Finally, the energy distribution is obtained for different cation arrangements in MgAl$_2$O$_4$ spinel, for which long-range interactions are essential for the accurate description of its energetics.