A no-pair formalism employing external-field projection operators correct to second order in the potential is used to calculate the 1s energies of one-electron atoms and ground-state properties of the bromine and silver atoms in the framework of the multireference double-excitation configuration-interaction (MRD-CI) method. It is found that the relativistic two-component method that has been used reproduces the one-particle energies of the Dirac equation to order (Zα${)}^3$. The operator is bounded from below and can be used variationally in relativistic electron-structure calculations of many-electron atoms and molecules. The relativistic correction to the total energy recovers 97% of the relativistic correction of the Dirac-Hartree-Fock (DHF) result in the case of the bromine atom and more than 99% in the case of the silver atom. The relativistic correction of the ionization potential of silver has been calculated to be 0.47 eV at the CI level, in good agreement with DHF results, the correlation contribution in the relativistic case being 0.42 eV. The remaining discrepancy of the absolute value of 6.85 eV (DHF 6.34 eV) to experiment (7.57 eV) is attributed to basis-set deficiencies. The corresponding CI value of the electron affinity (relativistic CI value 1.05 eV, nonrelativistic 0.90 eV) is in much better agreement with experiment (1.30 eV). It is found that correlation contribution and relativistic effects are nonadditive.

• Received 16 January 1986

DOI:https://doi.org/10.1103/PhysRevA.33.3742