Numerical analysis of the planewave discretization of orbital-free and Kohn-Sham models Part I: The Thomas-Fermi-von Weizacker model

TL;DR

This paper provides error estimates for planewave discretizations of the Thomas-Fermi-von Weizsacker and Kohn-Sham models, crucial for accurate simulations of molecular systems in condensed phases.

Contribution

It offers the first comprehensive a priori error analysis for the spectral and pseudospectral planewave methods applied to these models, especially addressing the convexity of the TFW model.

Findings

Error bounds for spectral and pseudospectral discretizations

Existence and uniqueness of minimizers for large energy cut-offs

Validation of the models' applicability to condensed phase systems

Abstract

We provide {\it a priori} error estimates for the spectral and pseudospectral Fourier (also called planewave) discretizations of the periodic Thomas-Fermi-von Weizs\"acker (TFW) model and of the Kohn-Sham model, within the local density approximation (LDA). These models allow to compute approximations of the ground state energy and density of molecular systems in the condensed phase. The TFW model is stricly convex with respect to the electronic density, and allows for a comprehensive analysis (Part I). This is not the case for the Kohn-Sham LDA model, for which the uniqueness of the ground state electronic density is not guaranteed. Under a coercivity assumption on the second order optimality condition, we prove in Part II that for large enough energy cut-offs, the discretized Kohn-Sham LDA problem has a minimizer in the vicinity of any Kohn-Sham ground state, and that this minimizer is unique up to unitary transform. We then derive optimal {\it a priori} error estimates for both the spectral and the pseudospectral discretization methods.