Application of accurate MP2 energies for closed‐shell atoms in examinations of density functionals for 3d10 electron ions

Abstract

AbstractArguments are presented that accurate second‐order Møller–Plesset (MP2) energies, evaluated in calculations involving extensive radial and angular basis sets, followed by careful angular extrapolations (referred to as MP2/CA energies), provide reliable approximations to the correlation energies for the ground states of closed‐shell atomic systems. MP2/CA energies are calculated for the members of the Cu+ isoelectronic series (Cu+, Zn2+, Ge4+, and Kr8+), which belong to the simplest atomic system containing the 3d10 configuration. The most accurate ab initio correlation energies for a 28‐electron isoelectronic series are reported. To exemplify the applicability of the total nonrelativistic energies, obtained as a sum of these energies and accurate Hartree–Fock energies, in examinations of density functionals, density functional theory energies are calculated for various functionals and basis sets and compared with their MP2/CA counterparts. An evaluation of the performance of these functionals is presented. The impact of the limited basis set size on the energy results is estimated. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2004