Reduction of Hartree-Fock Wavefunctions to Kohn-Sham Effective Potentials Using Multiresolution Analysis

We present a highly accurate numerical implementation for computing the Kohn-Sham effective potentials for molecules based on a Hartree-Fock wavefunction and density, following the RKS approach of Staroverov and co-workers [J. Chem. Phys. 2014, 140, 18A535]. Potentials and orbitals are represented in a multiresolution wavelet basis, avoiding basis set incompleteness-related issues. Together with the RKS method, the often occurring problems of oscillating potentials are removed. The MRA implementation of the RKS method allows the generation of molecular Kohn-Sham potentials of benchmark quality. Numerical data for atoms up to Kr and a number of molecules are given, with a special emphasis on the role of nodal planes in the calculations, as showcased in HCN and benzene.

Automated summary

This study presents a highly accurate numerical implementation for computing molecular Kohn-Sham effective potentials based on a Hartree-Fock wavefunction and density, using the RKS approach. The method represents potentials and orbitals in a multiresolution wavelet basis to avoid issues related to basis set incompleteness, and successfully removes oscillating potentials. The implementation allows for the generation of benchmark quality molecular Kohn-Sham potentials, with a special emphasis on the role of nodal planes in calculations demonstrated in HCN and benzene.