Nonparametric Local Pseudopotentials with Machine Learning: A Tin Pseudopotential Built Using Gaussian Process Regression

J Phys Chem A. 2020 Dec 31;124(52):11111-11124. doi: 10.1021/acs.jpca.0c05723. Epub 2020 Dec 18.

Abstract

We present novel nonparametric representation math for local pseudopotentials (PP) based on Gaussian Process Regression (GPR). Local pseudopotentials are needed for materials simulations using Orbital-Free Density Functional Theory (OF-DFT) to reduce computational cost and to allow kinetic energy functional (KEF) application only to the valence density. Moreover, local PPs are important for the development of accurate KEFs for OF-DFT, but they are only available for a limited number of elements. We optimize local PPs of tin (Sn) represented with GPR to reproduce the experimental lattice constants of α- and β-Sn and the energy difference between these two phases as well as their electronic structure and charge density distributions which are obtained with Kohn-Sham Density Functional Theory employing semilocal PPs. The use of a nonparametric GPR-based PP representation avoids difficulties associated with the use of parametrized functions and has the potential to construct an optimal local PP independent of prior assumptions. The GPR-based Sn local PP results in well-reproduced bulk properties of α- and β-tin and electronic valence densities similar to those obtained with semilocal PP.