Coarse Grained Density Functional Theories for Metallic Alloys: Generalized Coherent Potential Approximations and Charge Excess Functional Theory

TL;DR

This paper introduces a class of generalized coherent potential approximations (GCPA) within density functional theory for metallic alloys, offering computational efficiency and accurate results comparable to full-potential calculations.

Contribution

It develops a unified GCPA framework for metallic alloys, deriving a generalized Charge Excess Functional (CEF) theory with multipolar interactions, and demonstrates its accuracy against state-of-the-art calculations.

Findings

GCPA density functional is computationally efficient with O(N) scalability.

GCPA and CEF results closely match LAPW calculations for site charges and energies.

The generalized CEF includes multipolar interactions, improving modeling accuracy.

Abstract

The class of the Generalized Coherent Potential Approximations (GCPA) to the Density Functional Theory (DFT) is introduced within the Multiple Scattering Theory formalism for dealing with, ordered or disordered, metallic alloys. All GCPA theories are based on a common ansatz for the kinetic part of the Hohenberg-Kohn functional and each theory of the class is specified by an external model concerning the potential reconstruction. The GCPA density functional consists of marginally coupled local contributions, does not depend on the details of the charge density and can be exactly rewritten as a function of the appropriate charge multipole moments associated with each lattice site. A general procedure based on the integration of the 'qV' laws is described that allows for the explicit construction the same function. The coarse grained nature of the GCPA density functional implies great computational advantages and is connected with the O(N) scalability of GCPA algorithms. Moreover, it is shown that a convenient truncated series expansion of the GCPA functional leads to the Charge Excess Functional (CEF) theory [E. Bruno, L. Zingales and Y. Wang, Phys. Rev. Lett. {\bf 91}, 166401 (2003)] which here is offered in a generalized version that includes multipolar interactions. CEF and the GCPA numerical results are compared with status of art LAPW full-potential density functional calculations for 62, bcc- and fcc-based, ordered CuZn alloys, in all the range of concentrations. These extensive tests show that the discrepancies between GCPA and CEF are always within the numerical accuracy of the calculations, both for the site charges and the total energies. Furthermore, GCPA and CEF very carefully reproduce the LAPW site charges and the total energy trends.