Accurate Anisotropic Gaussian Type Orbital Basis Sets for Atoms in Strong Magnetic Fields

TL;DR

This paper develops a new, efficient method for constructing highly accurate anisotropic Gaussian basis sets for atoms in strong magnetic fields, improving computational efficiency while maintaining precision.

Contribution

It introduces a physics-based, formula-driven approach for generating AGTO basis sets that are adaptable to various atoms and magnetic field strengths, reducing basis set size and computational cost.

Findings

Achieves better than a few micro Hartree accuracy for single-electron systems.

Attains a few hundredths to a few millihartree accuracy for multi-electron atoms.

Residual basis set errors are significantly smaller than electronic correlation energies.

Abstract

In high magnetic field calculations, anisotropic Gaussian type orbital (AGTO) basis functions are capable of reconciling the competing demands of the spherically symmetric Coulombic interaction and cylindrical magnetic ($B$ field) confinement. However, the best available {\it a priori} procedure for composing highly accurate AGTO sets for atoms in a strong $B$ field [Phys.\ Rev. A {\bf 90}, 022504 (2014)] yields very large basis sets. Their size is problematical for use in any calculation with unfavorable computational cost scaling. Here we provide an alternative constructive procedure. It is based upon analysis of the underlying physics of atoms in $B$ fields that allows identification of several principles for the construction of AGTO basis sets. Aided by numerical optimization and parameter fitting, followed by fine tuning of fitting parameters, we devise formulae for generating accurate AGTO basis sets in an arbitrary $B$ field. For the hydrogen iso-electronic sequence, a set depends on $B$ field strength, nuclear charge, and upon orbital quantum numbers. For multi-electron systems, the basis set formulae also include adjustment to account for orbital occupations. Tests of the new basis sets for atoms H through C ($1 \le Z \le 6$), and ions Li$^+$, Be$^+$, and B$^+$, in a wide $B$ field range ($0 \le B \le 2000$ a.u.), show an accuracy better than a few $\mu$H for single-electron systems, and a few hundredths to a few mHs for multi-electron atoms. The relative errors are similar for different atoms and ions in a large $B$ field range, from a few to a couple of tens of millionths, thereby confirming rather uniform accuracy across the nuclear charge $Z$ and $B$ field strength values. Residual basis set errors are two to three orders of magnitude smaller than the electronic correlation energies in muti-electron atoms ...