Open-shell relativistic coupled-cluster method with Dirac-Fock-Breit wave functions: Energies of the gold atom and its cation

Abstract

The relativistic Fock-space coupled cluster method for the direct calculation of ionization potentials and excitation energies (including fine structure) is presented and applied to atomic Au and its ions. The no-pair Dirac-Coulomb-Breit Hamiltonian is taken as the starting point. The CCSD approximation is implemented (where CCSD indicates coupled cluster with single and double excitations), which includes single and double virtual excitations in a self-consistent manner, incorporating therefore the effects of the Coulomb and Breit interactions to all orders in these excitations. A rather large basis set (21s17p11d7f) of kinetically balanced Gaussian spinors is used to span the atomic orbitals. All calculated energies (ionization potential and electron affinity of Au, excitation energies of Au and ${\mathrm{Au}}^{+}$) agree with experiment to 0.1 eV or better, with an average error of 0.06 eV. Fine-structure splittings are accurate to better than 0.01 eV.