Physics-Driven Construction of Compact Primitive Gaussian Density Fitting Basis Sets

Kshitijkumar A. Surjuse; Edward F. Valeev

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arXiv · 2507.18471

Physics-Driven Construction of Compact Primitive Gaussian Density Fitting Basis Sets

Kshitijkumar A. Surjuse·Edward F. Valeev

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Abstract

We present model-assisted density fitting (MADF) basis set generator, an algorithm for generating primitive atomic Gaussian density fitting (DF) basis sets (DFBSs) from a contracted Gaussian orbital basis set (OBS). The MADF algorithm produces DFBSs suitable for accurate robust DF approximation of 2-particle interactions in mean-field and correlated electronic structure. The algorithm is designed to (a) saturate the OBS product space by a large regularized set of primitive solid-harmonic Gaussian shells with nonuniform distribution of exponents followed by (b) pruning of the shells according to their contributions to the 2-body energy of a correlated atomic ensemble. Building the DFBS generator model almost exclusively on mathematical and physical principles allows one to limit the number of parameters that control the density fitting error to three, with a single set of parameters sufficient for computations with all basis cardinal numbers, with and without correlation of core electrons, with and without scalar and spin-dependent relativistic effects, spanning almost all of the Periodic Table. Performance assessment included basis sets up to quadruple-zeta quality from several major basis set families, using molecules composed of main-group, d-block, and f-block elements. The resulting DF errors in Hartree-Fock and second-order MP2 energies (with relativistic all-electron treatments, when appropriate) were on the order of 20 and 10 microhartree per electron, respectively.

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Kshitijkumar A. Surjuse, Edward F. Valeev. 2025-10-10. Physics-Driven Construction of Compact Primitive Gaussian Density Fitting Basis Sets. https://arxiv.org/abs/2507.18471

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