Clifford Boundary Conditions for Periodic Systems: the Madelung Constant of Cubic Crystals in 1, 2 and 3 Dimensions

TL;DR

This paper presents a robust, efficient real-space method using Clifford torus topology to accurately compute Madelung constants in periodic cubic crystal systems across 1, 2, and 3 dimensions, with low computational cost.

Contribution

The authors introduce a novel real-space approach employing Clifford boundary conditions that improves accuracy and efficiency in calculating Madelung constants for periodic systems.

Findings

Method achieves high accuracy with low computational effort.

Convergence to reference values is consistent across supercell shapes.

Scales linearly with the number of atoms, enabling quick calculations.

Abstract

In this work we demonstrate the robustness of a real-space approach for the treatment of infinite systems described with periodic boundary conditions that we have recently proposed [J. Phys. Chem. Lett. 17, 7090]. In our approach we extract a fragment, i.e., a supercell, out of the infinite system, and then modifying its topology into the that of a Clifford torus which is a flat, finite and border-less manifold. We then renormalize the distance between two points by defining it as the Euclidean distance in the embedding space of the Clifford torus. With our method we have been able to calculate the reference results available in the literature with a remarkable accuracy, and at a very low computational effort. In this work we show that our approach is robust with respect to the shape of the supercell. In particular, we show that the Madelung constants converge to the same values but that the convergence properties are different. Our approach scales linearly with the number of atoms. The calculation of Madelung constants only takes a few seconds on a laptop computer for a relative precision of about 10$^{-6}$.