Nested Gausslet Basis Sets

TL;DR

This paper introduces nested gausslet bases and hybrid Gaussian-gausslet bases that enable efficient, high-accuracy Hartree-Fock calculations for large atomic systems by simplifying electron-electron interactions.

Contribution

It presents novel nested gausslet bases, pure Gaussian distorted gausslet bases, and hybrid bases, along with new mathematical insights into their construction and properties.

Findings

Achieved 2×10^{-5} Ha accuracy for neon atom Hartree-Fock energy.

Demonstrated bases allow fast calculations with small matrices (~10^4 elements).

Proved a theorem linking basis set properties: completeness, orthogonality, zero-moments, and diagonalization.

Abstract

We introduce nested gausslet (NG) bases, an improvement on previous gausslet bases which can treat systems containing atoms with much larger atomic number. We also introduce pure Gaussian distorted gausslet bases, which allow the Hamiltonian integrals to be performed analytically, as well as hybrid bases in which the gausslets are combined with standard Gaussian-type bases. All these bases feature the diagonal approximation for the electron-electron interactions, so that the Hamiltonian is completely defined by two $N_b\times N_b$ matrices, where $N_b \approx 10^4$ is small enough to permit fast calculations at the Hartree-Fock level. In constructing these bases we have gained new mathematical insight into the construction of one-dimensional diagonal bases. In particular we have proved an important theorem relating four key basis set properties: completeness, orthogonality, zero-moment conditions, and diagonalization of the coordinate operator matrix. We test our basis sets on small systems with a focus on high accuracy, obtaining, for example, an accuracy of $2\times10^{-5}$ Ha for the total Hartree-Fock energy of the neon atom in the complete basis set limit.