Nonlocal Pseudopotential Energy Density Functional for Orbital-Free Density Functional Theory

TL;DR

This paper introduces a novel theoretical framework that enables the use of nonlocal pseudopotentials in orbital-free density functional theory, improving accuracy and transferability for large-scale material simulations.

Contribution

It develops a new energy density functional derived from nonlocal pseudopotentials projected onto the non-interacting density matrix, challenging previous limitations.

Findings

Enables direct use of nonlocal pseudopotentials in OF-DFT

Improves transferability and accuracy over local pseudopotentials

Creates a new theoretical framework surpassing traditional OF-DFT methods

Abstract

Orbital-free density functional theory (OF-DFT) runs at low computational cost that scales linearly with the number of simulated atoms, making it suitable for large-scale material simulations. It is generally considered that OF-DFT strictly requires the use of local pseudopotentials, rather than orbital-dependent nonlocal pseudopotentials, for the calculation of electron-ion interaction energies, as no orbitals are available. This is unfortunate situation since the nonlocal pseudopotentials are known to give much better transferability and calculation accuracy than local ones. We report here the development of a theoretical scheme that allows the direct use of nonlocal pseudopotentials in OF-DFT. In this scheme, a nonlocal pseudopotential energy density functional is derived by the projection of nonlocal pseudopotential onto the non-interacting density matrix (instead of 'orbitals') that can be approximated explicitly as a functional of electron density. Our development defies the belief that nonlocal pseudopotentials are not applicable to OF-DFT, leading to the creation of an alternate theoretical framework of OF-DFT that works superior to the traditional one.