Past exam of the chemistry course of the year 3 of the natural sciences course of the University of Cambridge / 2021 / Paper 2A / Section B / 24 / c

Restricted Hartree–Fock incorrectly retains ionic configurations when a homonuclear bond dissociates. As overlap vanishes, its symmetry-preserving occupied orbital approaches $({\varphi }_A+{\varphi }_B)/\sqrt{2}$. The doubly occupied spatial product containsThe first and last terms place both electrons on one separated atom. Their combined probability remains one half, while the correct neutral singlet has one electron on each atom. The resulting spurious Coulomb repulsion raises the restricted dissociation limit. This is missing static electron correlation, not a failure of the Born-Oppenheimer approximation.

A two-configuration expansion using both ${\sigma }_g^2$ and ${\sigma }_u^2$ can cancel the ionic terms and recover the Heitler–London separated-atom singlet. Configuration interaction in the appropriate active space or a multiconfigurational self-consistent treatment supplies this remedy. The Unrestricted Hartree-Fock method can instead localize opposite spins on different atoms and give the correct separated-atom energy, but its single determinant breaks spin symmetry and is not the pure singlet at intermediate separation. The distinction between restricted and symmetry-broken descriptions of stretched hydrogen is treated in the original analysis of Coulson and Fischer.^[ref]

No: the lowest dissociation channel is $\mathrm{He}+{\mathrm{H}}^{+}$, which a doubly occupied helium-centred orbital can describe. In the heteronuclear molecular orbital diagram the helium $1s$ site lies below the hydrogen $1s$ site. As separation grows, the bonding orbital tends to helium $1s$, the antibonding orbital tends to hydrogen $1s$, and the two ground-state electrons remain in the lower orbital.

There is therefore no symmetry requirement to keep both sites equally occupied and no compulsory half-weight mixture of wrong ionic configurations at dissociation. The physical asymptote is already a closed-shell atom plus a bare proton. The alternative ${\mathrm{He}}^{+}+\mathrm{H}$ limit lies higher. A Restricted Hartree-Fock method curve approaches the Hartree–Fock helium energy rather than the exact correlated helium energy, so ordinary dynamic electron correlation is still missing, but this is not the homonuclear static-correlation catastrophe. In the preceding two-panel sketch, the helium hydride curves have the same qualitative dissociation channel with a small residual correlation offset, whereas the hydrogen restricted curve reaches a qualitatively wrong high limit.