TY - JOUR
T1 - Ground state of two electrons on concentric spheres
AU - Loos, Pierre François
AU - Gill, Peter M.W.
PY - 2010/5/19
Y1 - 2010/5/19
N2 - We extend our analysis of two electrons on a sphere to electrons on concentric spheres with different radii. The strengths and weaknesses of several electronic structure models are analyzed, ranging from the mean-field approximation (restricted and unrestricted Hartree-Fock solutions) to configuration interaction expansion, leading to near-exact wave functions and energies. The Møller-Plesset energy corrections (up to third-order) and the asymptotic expansion for the large-sphere regime are also considered. We also study the position intracules derived from approximate and exact wave functions. We find evidence for the existence of a long-range Coulomb hole in the large-sphere regime and infer that unrestricted Hartree-Fock theory overlocalizes the electrons.
AB - We extend our analysis of two electrons on a sphere to electrons on concentric spheres with different radii. The strengths and weaknesses of several electronic structure models are analyzed, ranging from the mean-field approximation (restricted and unrestricted Hartree-Fock solutions) to configuration interaction expansion, leading to near-exact wave functions and energies. The Møller-Plesset energy corrections (up to third-order) and the asymptotic expansion for the large-sphere regime are also considered. We also study the position intracules derived from approximate and exact wave functions. We find evidence for the existence of a long-range Coulomb hole in the large-sphere regime and infer that unrestricted Hartree-Fock theory overlocalizes the electrons.
UR - http://www.scopus.com/inward/record.url?scp=77953225362&partnerID=8YFLogxK
U2 - 10.1103/PhysRevA.81.052510
DO - 10.1103/PhysRevA.81.052510
M3 - Article
SN - 1050-2947
VL - 81
JO - Physical Review A - Atomic, Molecular, and Optical Physics
JF - Physical Review A - Atomic, Molecular, and Optical Physics
IS - 5
M1 - 052510
ER -