English

Predicting complete basis set limit quasiparticle energies from triple-$\zeta$ calculations

Chemical Physics 2025-12-01 v1

Abstract

We present a simple linear model to estimate the basis set incompleteness errors (BSIE) of (vertex-corrected) GWGW QP energies based on the kinetic energy of the corresponding orbital only. We parametrise the model for G0W0G_0W_0, quasi-particle self-consistent GWGW (qsGWGW), and vertex-corrected (ΣBSE@LBSE\Sigma^{BSE}@L^{BSE}) QP energies on a large set of molecules containing 10 different elements for which we calculate complete basis set (CBS) limit extrapolated reference values with correlation-consistent basis sets ranging from triple- to hextuple-ζ\zeta (TZ/6Z). Based on these accurate reference values, we obtain model parameters for Gaussian-type and Slater-type orbital (GTO/STO) basis sets which allow for the extrapolation of QP energies calculated with TZ basis sets to the CBS limit with errors of 20 to 30 meV. Analysing extrapolation errors, we show the commonly used extrapolation method which assumes an inverse linear dependence of the BSIE on the inverse number of basis functions to be valid, but to produce larger errors, even when a quadruple-ζ\zeta calculation is used in the extrapolation.

Keywords

Cite

@article{arxiv.2511.22462,
  title  = {Predicting complete basis set limit quasiparticle energies from triple-$\zeta$ calculations},
  author = {Dario Baum and Lucas Visscher and Arno Förster},
  journal= {arXiv preprint arXiv:2511.22462},
  year   = {2025}
}