English

Variational Dirac-Coulomb explicitly correlated computations for atoms and molecules

Chemical Physics 2022-03-14 v4 Quantum Physics

Abstract

The Dirac-Coulomb equation with positive-energy projection is solved using explicitly correlated Gaussian functions. The algorithm and computational procedure aims for a parts-per-billion convergence of the energy to provide a starting point for further comparison and further developments in relation with high-resolution atomic and molecular spectroscopy. Besides a detailed discussion of the implementation of the fundamental spinor structure, permutation and point-group symmetries, various options for the positive-energy projection procedure are presented. The no-pair Dirac-Coulomb energy converged to a parts-per-billion precision is compared with perturbative results for atomic and molecular systems with small nuclear charge numbers. The subsequent paper [Paper II: D. Ferenc, P. Jeszenszki, and E. M\'atyus (2022)] describes the implementation of the Breit interaction in this framework.

Keywords

Cite

@article{arxiv.2110.06638,
  title  = {Variational Dirac-Coulomb explicitly correlated computations for atoms and molecules},
  author = {Péter Jeszenszki and Dávid Ferenc and Edit Mátyus},
  journal= {arXiv preprint arXiv:2110.06638},
  year   = {2022}
}
R2 v1 2026-06-24T06:51:21.744Z