Variational versus perturbative relativistic energies for small and light atomic and molecular systems

Abstract

Variational and perturbative relativistic energies are computed and compared for two-electron atoms and molecules with low nuclear charge numbers. In general, good agreement of the two approaches is observed. Remaining deviations can be attributed to higher-order relativistic, also called non-radiative quantum electrodynamics (QED), corrections of the perturbative approach that are automatically included in the variational solution of the no-pair Dirac$-$Coulomb$-$Breit (DCB) equation to all orders of the $α$ fine-structure constant. The analysis of the polynomial $α$ dependence of the DCB energy makes it possible to determine the leading-order relativistic correction to the non-relativistic energy to high precision without regularization. Contributions from the Breit$-$Pauli Hamiltonian, for which expectation values converge slowly due the singular terms, are implicitly included in the variational procedure. The $α$ dependence of the no-pair DCB energy shows that the higher-order ($α^4 E_\mathrm{h}$) non-radiative QED correction is 5 % of the leading-order ($α^3 E_\mathrm{h}$) non-radiative QED correction for $Z=2$ (He), but it is 40 % already for $Z=4$ (Be$^{2+}$), which indicates that resummation provided by the variational procedure is important already for intermediate nuclear charge numbers.