Electronic Structure Calculation with the Exact Pseudopotential and Interpolating Wavelet Basis

TL;DR

This paper introduces the exact pseudopotential (EPP) combined with an interpolating wavelet basis for electronic structure calculations, demonstrating improved accuracy over traditional methods for small atoms.

Contribution

The paper presents the novel EPP approach integrated with a wavelet Galerkin method, effectively removing Coulomb singularity issues in atomic orbital calculations.

Findings

EPP-Galerkin method achieves higher accuracy than finite-difference methods.

EPP effectively removes Coulomb singularity in atomic calculations.

Method successfully computes orbitals for small atoms with improved precision.

Abstract

Electronic structure calculations are mostly carried out with Coulomb potential singularity adapted basis sets like STO or contracted GTO. With other basis or for heavy elements the pseudopotentials may appear as a practical alternative. Here, we introduce the exact pseudopotential (EPP) to remove the Coulomb singularity and test it for orbitals of small atoms with the interpolating wave basis set. We apply EPP to the Galerkin method with a basis set consisting of Deslauriers--Dubuc scaling functions on the half-infinite real interval. We demonstrate the EPP--Galerkin method by computing the hydrogen atom 1s, 2s, and 2p orbitals and helium atom configurations $\mathrm{He\;1s^2}$, $\mathrm{He\;1s2s\;{}^1 S}$, and $\mathrm{He\;1s2s\;{}^3 S}$. We compare the method to the ordinary interpolating wavelet Galerkin method (OIW--Galerkin) handling the singularity at the nucleus by excluding the scaling function located at the origin from the basis. We also compare the performance of our approach to that of finite--difference approach, which is another practical method for spherical atoms. We find the accuracy of the EPP--Galerkin method better than both of the above mentioned methods.