Importance profiles. Visualization of atomic basis set requirements

Abstract

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 limit: the importance of a normalized AO basis function | α ⟩ centered on some nucleus can be visualized by projecting | α ⟩ on the set of numerically represented occupied orbitals | ψ i ⟩ as I 0 ( α ) = ∑ i ⟨ α | ψ i ⟩ ⟨ ψ i | α ⟩ . Choosing α to be a continuous parameter describing the AO basis, such as the exponent of a Gaussian-type orbital or Slater-type orbital basis function, one is then able to visualize the importance of various functions. The proposed visualization I 0 ( α ) has the important property 0 ⩽ I 0 ( α ) ⩽ 1 which allows unambiguous interpretation. We also propose a straightforward generalization of the importance profile for polyatomic applications I ( α ) , in which the importance of a test function | α ⟩ 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.