Systematically Improvable Numerical Atomic Orbital Basis Using Contracted Truncated Spherical Waves

TL;DR

This paper introduces a new method for constructing numerical atomic orbital basis sets using contracted truncated spherical waves, improving transferability and accuracy in density functional theory calculations.

Contribution

It generalizes previous spillage minimization schemes by employing TSW basis functions, enhancing systematic improvability and transferability of NAOs.

Findings

Achieves satisfactory precision for molecular and bulk properties.

Improves description of conduction bands by including unoccupied states.

Reduces spurious interactions between periodic images.

Abstract

To solve the Kohn-Sham equation within the framework of density functional theory, we develop a scheme to construct numerical atomic orbital (NAO) basis sets by contracting truncated spherical waves (TSWs). The contraction minimizes the trace of the kinetic operator in the residual space, generalizing the spillage minimizing scheme [M. Chen et al., J. Phys. Condens. Matter 22, 445501 (2010); P. Lin et al., Phys. Rev. B 103, 235131 (2021)]. In addition to the systematic improvability inherited from previous schemes, the use of TSW instead of plane waves as the expansion basis bridges reference states and NAOs more effectively, and eliminates spurious interactions between periodic images, thereby enabling better transferability through the inclusion of extensive reference states. Benchmarks demonstrate that the constructed NAO achieves satisfactory precision for various properties of both molecules and bulk systems, including total energy, bond length, atomization energy, lattice constant, cohesive energy, band gap, and energy-level alignment. By incorporating unoccupied states, the improved transferability in describing the conduction band is demonstrated to be effective and substantial.