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A closed-shell coupled-cluster treatment of the Breit-Pauli first-order relativistic energy correction
Authors:Coriani Sonia  Helgaker Trygve  Jørgensen Poul  Klopper Wim
Institution:Dipartimento di Scienze Chimiche, Università degli Studi di Trieste, Via Licio Giorgieri 1, I-34127 Trieste, Italy.
Abstract:First-order relativistic corrections to the energy of closed-shell molecular systems are calculated, using all terms in the two-component Breit-Pauli Hamiltonian. In particular, we present the first implementation of the two-electron Breit orbit-orbit integrals, thus completing the first-order relativistic corrections within the two-component Pauli approximation. Calculations of these corrections are presented for a series of small and light molecules, at the Hartree-Fock and coupled-cluster levels of theory. Comparisons with four-component Dirac-Coulomb-Breit calculations demonstrate that the full Breit-Pauli energy corrections represent an accurate approximation to a fully relativistic treatment of such systems. The Breit interaction is dominated by the spin-spin interaction, the orbit-orbit interaction contributing only about 10% to the total two-electron relativistic correction in molecules consisting of light atoms. However, the relative importance of the orbit-orbit interaction increases with increasing nuclear charge, contributing more than 20% in H(2)S.
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