Structure of the correlation energy in 3d^{1}^{0} systems
Abstract
Thirdorder pair energies and the total thirdorder energy are obtained for the first time for an atomic system containing 3d electrons. The variationalperturbation method is applied within the framework of the RayleighSchrödinger perturbation theory with H_{0}=H_{HF}. The Nelectron firstorder wave function is defined in terms of orbital configurations of oneelectron functions and symmetryadapted pair functions in the form of partialwave (PW) expansions. Extensive basis sets including all PW up to l,l'≤9 are used. For Zn^{2}^{+} the total thirdorder energy amounts to about 9% of the secondorder energy obtained in the same basis set, which is considerably more than for closedshell tenelectron systems. Values of the energy functional for the function ψ_{0}+λψ_{1} are also reported. The latter represent the most accurate variational results obtained so far for atomic systems containing 3d electrons.
 Publication:

Journal of Chemical Physics
 Pub Date:
 June 1988
 DOI:
 10.1063/1.454326
 Bibcode:
 1988JChPh..88.7617J