Generalized relativistic small-core pseudopotentials accounting for quantum electrodynamic effects: construction and pilot applications

Abstract

A simple procedure to incorporate one-loop quantum electrodynamic (QED) corrections into the generalized (Gatchina) nonlocal shape-consistent relativistic pseudopotential model is described. The pseudopotentials for Lu, Tl, and Ra replacing only inner core shells (with principal quantum numbers $n\le 3$ for the two former elements and $n\le 4$ for the latter one) are derived from the solutions of reference atomic SCF problems with the Dirac-Coulomb-Breit Hamiltonian to which the model Lamb shift operator added. QED contributions to atomic valence excitation energies evaluated at the SCF level are demonstrated to exceed the errors introduced by the pseudopotential approximation itself by an order of magnitude. Pilot applications of the new model to calculations of excitation energies of two-valence-electron atomic systems using the intermediate-Hamiltonian relativistic Fock space coupled cluster method reformulated here for incomplete main model spaces are reported. Implications for high-accuracy molecular excited state calculations are discussed.

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Cited by in corpus (6)

• Theoretical molecular spectroscopy of actinide compounds: The ThO molecule
• Ground state of superheavy elements with $120\le Z\le 170$: systematic study of the electron-correlation, Breit, and QED effects
• Challenges with relativistic GW calculations in solids and molecules
• Ab initio study of electronic states and radiative properties of the AcF molecule
• Relativistic atomic structure calculations in support of spectroscopy
• Optical cycling in charged complexes with Ra-N bonds