Accounting for Breit interaction in actinide and superheavy element compounds: 1. General remarks

Abstract

The incorporation of the Breit interaction in atomic and molecular calculations is discussed in the framework of four-component all-electron and two-component relativistic effective core potential (RECP)formalisms. Contributions of the Breit interaction between different core and valence shells are studied in the Dirac-Fock approximation for the uranium, plutonium, ekathallium (Z=113), ekalead (Z=114) and other heavy atoms. It is shown that the two-electron Breit effects between the valence electrons can be neglected for "chemical accuracy" (1 kcal/mol) of calculation of spectroscopic properties of systems containing superheavy elements and actinides whereas large core-core and core-valence Breit contributions can be efficiently described by one-electron RECP operators. Different versions of the generalized RECPs with the Breit interaction taken into account are constructed for uranium and plutonium and tested in comparison with the corresponding all-electron four-component calculations.