Importance profiles. Visualization of atomic basis set requirements

TL;DR

This paper introduces a visualization method for atomic orbital basis set importance profiles using fully numerical wave functions, aiding in understanding basis set requirements for molecules.

Contribution

It proposes a new importance profile visualization technique based on projections onto numerical wave functions, enabling assessment of basis set adequacy.

Findings

Importance profiles range between 0 and 1, allowing clear interpretation.

Profiles effectively visualize basis set requirements for atoms and molecules.

Method demonstrated on atoms and diatomic molecules with diverse chemical properties.

Abstract

Recent developments in fully numerical methods promise interesting opportunities for new, compact atomic orbital (AO) basis sets that maximize the overlap to fully numerical reference wave functions, following the pioneering work of Richardson and coworkers from the early 1960s. Motivated by this technique, we suggest a way to visualize the importance of AO basis functions employing fully numerical wave functions computed at the complete basis set (CBS) limit: the importance of a normalized AO basis function $|\alpha\rangle$ centered on some nucleus can be visualized by projecting $|\alpha\rangle$ on the set of numerically represented occupied orbitals $|\psi_{i}\rangle$ as $I_{0}(\alpha)=\sum_{i}\langle\alpha|\psi_{i}\rangle\langle\psi_{i}|\alpha\rangle$. Choosing $\alpha$ to be a continuous parameter describing the orbital basis, such as the exponent of a Gaussian-type orbital (GTO) or Slater-type orbital (STO) basis function, one is then able to visualize the importance of various functions. The proposed visualization $I_{0}(\alpha)$ has the important property $0\leq I_{0}(\alpha)\leq1$ which allows unambiguous interpretation. We also propose a straightforward generalization of the importance profile for polyatomic appliations $I(\alpha)$, in which the importance of a test function $|\alpha\rangle$ is measured as the increase in projection from the atomic minimal basis. We exemplify the methods with importance profiles computed for atoms from the first three rows, and for a set of chemically diverse diatomic molecules. We find that the importance profile offers a way to visualize the atomic basis set requirements for a given system in an a priori manner, provided that a fully numerical reference wave function is available.