Systematically convergent method for accurate total energy calculations with localized atomic orbitals

TL;DR

This paper presents a new systematic method for electronic structure calculations with localized atomic orbitals that reliably converges to the complete basis set limit without extrapolation, demonstrated on benzene.

Contribution

The authors introduce a stable, controlled approach for CBS limit convergence in localized atomic orbital calculations, enabling large basis sets and improved accuracy.

Findings

Perfect agreement with standard methods for small basis sets

Efficient handling of very large basis sets without instability

Achieved lowest variational energies near CBS limit in VMC and LRDMC

Abstract

We introduce a method for solving a self consistent electronic calculation within localized atomic orbitals, that allows us to converge to the complete basis set (CBS) limit in a stable, controlled, and systematic way. We compare our results with the ones obtained with a standard quantum chemistry package for the simple benzene molecule. We find perfect agreement for small basis set and show that, within our scheme, it is possible to work with a very large basis in an efficient and stable way. Therefore we can avoid to introduce any extrapolation to reach the CBS limit. In our study we have also carried out variational Monte Carlo (VMC) and lattice regularized diffusion Monte Carlo (LRDMC) with a standard many-body wave function (WF) defined by the product of a Slater determinant and a Jastrow factor. Once the Jastrow factor is optimized by keeping fixed the Slater determinant provided by our new scheme, we obtain a very good description of the atomization energy of the benzene molecule only when the basis of atomic orbitals is large enough and close to the CBS limit, yielding the lowest variational energies.