Accurate atomic correlation and total energies for correlation consistent effective core potentials

TL;DR

This paper provides highly accurate total energy calculations for correlation consistent effective core potentials (ccECPs) across H-Kr elements, serving as benchmarks for future quantum chemistry and condensed matter studies.

Contribution

It introduces benchmark total energies for ccECPs using advanced many-body methods, improving accuracy and transferability for electronic structure calculations.

Findings

Achieved 1-10 mHa accuracy for K-Zn atoms

Estimated complete basis set limits for various methods

Provided fixed-node DMC energies to assess biases

Abstract

Very recently, we introduced a set of correlation consistent effective core potentials (ccECPs) constructed within full many-body approaches. By employing significantly more accurate correlated approaches we were able to reach a new level of accuracy for the resulting effective core Hamiltonians. We also strived for simplicity of use and easy transferability into a variety of electronic structure methods in quantum chemistry and condensed matter physics. Here, as a reference for future use, we present exact or nearly-exact total energy calculations for these ccECPs. The calculations cover H-Kr elements and are based on the state-of-the-art configuration interaction (CI), coupled-cluster (CC), and quantum Monte Carlo (QMC) calculations with systematically eliminated/improved errors. In particular, we carry out full CI/CCSD(T)/CCSDT(Q) calculations with cc-pVnZ with up to n=6 basis sets and we estimate the complete basis set limits. Using combinations of these approaches, we achieved an accuracy of $\approx$ 1-10 mHa for K-Zn atoms and $\approx$ 0.1-0.3 mHa for all other elements $-$ within about 1% or better of the ccECP total correlation energies. We also estimate the corresponding kinetic energies within the feasible limit of full CI calculations. In order to provide data for QMC calculations, we include fixed-node diffusion Monte Carlo energies for each element that give quantitative insights into the fixed-node biases for single-reference trial wave functions. The results offer a clear benchmark for future high accuracy calculations in a broad variety of correlated wave function methods such as CI and CC as well is in stochastic approaches such as real space sampling QMC.