Nested gausslet basis sets

Abstract

We introduce nested gausslet bases, an improvement on previous gausslet bases that can treat systems containing atoms with much larger atomic numbers. We also introduce pure Gaussian distorted gausslet bases, which allow the Hamiltonian integrals to be performed analytically, as well as hybrid bases in which the gausslets are combined with standard Gaussian-type bases. All these bases feature the diagonal approximation for the electron–electron interactions so that the Hamiltonian is completely defined by two Nb × Nb matrices, where Nb ≈ 104 is small enough to permit fast calculations at the Hartree–Fock level. In constructing these bases, we have gained new mathematical insight into the construction of one-dimensional diagonal bases. In particular, we have proved an important theorem relating four key basis set properties: completeness, orthogonality, zero-moment conditions, and diagonalization of the coordinate operator matrix. We test our basis sets on small systems with a focus on high accuracy, obtaining, for example, an accuracy of 2 × 10−5 Ha for the total Hartree–Fock energy of the neon atom in the complete basis set limit.