Variational Dirac-Coulomb explicitly correlated computations for atoms and molecules

摘要

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. describes the implementation of the Breit interaction in this framework. Published under an exclusive license by AIP Publishing.