A correlation functional that is termed exact-exchange random phase approximation (EXX-RPA) functional and is obtained with the exact frequency-dependent exchange kernel via the fluctuation-dissipation theorem is shown to correctly describe electron pair bonds in the dissociation limit without the need to resort to symmetry breaking in spin space. Because the functional also yields more accurate electronic energies for molecules in their equilibrium geometry than standard correlation functionals, it combines accuracy at equilibrium bond distances and in dissociation processes with a correct description of spin, something all commonly employed correlation functionals fail to do. The reason why the EXX-RPA correlation functional yields distinctively and qualitatively better results than RPA approaches based on Hartree-Fock and time-dependent Hartree-Fock is explained.

• Received 24 September 2010

DOI:https://doi.org/10.1103/PhysRevLett.106.093001