Atomic Mean-Field Approach within Exact Two-Component Theory Based on the Dirac–Coulomb–Breit Hamiltonian

Abstract

An extension of the exact two-component theory with atomic mean-field integrals (the X2CAMF scheme) to the treatment of the Breit term together with efficient implementation using an atomic Dirac-Coulomb-Breit Hartree-Fock program is reported. The accuracy of the X2CAMF scheme for treating the contributions from the Breit term to the molecular properties is demonstrated using benchmark calculations of equilibrium bond lengths, harmonic frequencies, and dipole moments for molecules containing elements across the periodic table. Calculations of the properties for molecules containing period four elements aiming at high accuracy as well as for Th- and U-containing molecules are also presented and compared with experimental results to demonstrate the usefulness of the X2CAMF scheme in combination with accurate treatments of electron correlation by the coupled-cluster (CC) methods. The combination of CC methods and the X2CAMF scheme shows potential to extend the accuracy of CC calculations to heavy elements, e.g., to computational heavy-element thermochemistry.