Straightforward and Accurate Automatic Auxiliary Basis Set Generation for Molecular Calculations with Atomic Orbital Basis Sets.

Abstract

Density fitting (DF), also known as the resolution of the identity (RI), is a widely used technique in quantum chemical calculations with various types of atomic basis sets─Gaussian-type orbitals, Slater-type orbitals, as well as numerical atomic orbitals─to speed up density functional, Hartree-Fock (HF), and post-HF calculations. Traditionally, custom auxiliary basis sets are hand-optimized for each orbital basis set; however, some automatic schemes have also been suggested. In this work, we propose a simple yet numerically stable automated scheme for forming auxiliary basis sets with the help of a pivoted Cholesky decomposition, which is applicable to any type of atomic basis function. We exemplify the scheme with proof-of-concept calculations with Gaussian basis sets and show that the proposed approach leads to negligible DF/RI errors in HF and second-order Møller-Plesset (MP2) total energies of the non-multireference part of the W4-17 test set when used with orbital basis sets of at least polarized triple-ζ quality. The results are promising for future applications employing Slater-type orbitals or numerical atomic orbitals, as well as schemes based on the use of local fitting approaches. Global fitting approaches can also be used, in which case the high-angular-momentum functions produced by the present scheme can be truncated to minimize the computational cost.