Variational determination of the second-order density matrix for the isoelectronic series of beryllium, neon, and silicon

Abstract

The isoelectronic series of Be, Ne, and Si are investigated using a variational determination of the second-order density matrix. A semidefinite program was developed that exploits all rotational and spin symmetries in the atomic system. We find that the method is capable of describing the strong static electron correlations due to the incipient degeneracy in the hydrogenic spectrum for increasing central charge. Apart from the ground-state energy, various other properties are extracted from the variationally determined second-order density matrix. The ionization energy is constructed using the extended Koopmans' theorem. The natural occupations are also studied, as well as the correlated Hartree-Fock-like single-particle energies. The exploitation of symmetry allows to study the basis set dependence and results are presented for correlation-consistent polarized valence double, triple, and quadruple zeta basis sets.