Abstract
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.
| Original language | English |
|---|---|
| Article number | 052510 |
| Journal | Physical Review A - Atomic, Molecular, and Optical Physics |
| Volume | 81 |
| Issue number | 5 |
| DOIs | |
| Publication status | Published - 19 May 2010 |
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