Large-scale pseudopotential density functional theory calculations using orthogonalized enriched finite element basis

Abstract

We present an efficient and scalable computational framework for pseudopotential Kohn-Sham density functional theory (KS-DFT) calculations using an enriched finite element (EFE) basis. The EFE basis is formed by augmenting the classical finite element (CFE) basis with compact atom-centered functions, which we term enrichment functions. The key idea is to combine the completeness of a finite element basis with the efficiency of an atom-centered basis. We orthogonalize the enrichment functions with respect to the underlying CFE basis to simultaneously improve the conditioning of the EFE basis and the efficiency of evaluating the inverse of the overlap matrix. To efficiently solve the Kohn-Sham eigenvalue problem, we employ a residual-based Chebyshev subspace iteration approach that is tolerant to approximations in the evaluation of the inverse of the overlap matrix. We demonstrate the accuracy of the framework as compared to the widely available DFT packages. For benchmark non-periodic calculations, ranging up to 39,083 electrons, the EFE basis offers a $5-7\times$ reduction in degrees of freedom over the CFE basis. As a result of this, EFE achieves a $5-9\times$ reduction in computational cost over the CFE basis. The EFE basis also provides a $4-5\times$ reduction in the required memory compared to the CFE basis, thus allowing for optimal utilization of computational resources. Finally, we demonstrate that the EFE basis affords good parallel scalability. Overall, the EFE basis offers a systematically convergent, fast, scalable, resource-efficient basis for pseudopotential DFT calculations.