Past exam of the advanced quantum physics course of the University of Cambridge / 2021 / Section B / 6 / c / Solution

Each one-particle energy eigenstate has definite parity about the centre of the well, so $⟨n|x|n⟩=0$. Consequently, a doubly occupied orbital has $⟨x_1{x}_2⟩=0$. For distinct orbitals, the two off-diagonal exchange terms instead survive:The position matrix elements in a symmetric infinite square well, with the present width $a$, giveThe sign of $x_{12}$ depends on the orbital phase convention, while $D$ does not. The perturbation acts only on the spatial part and cannot mix orthogonal singlet states and triplet states. Within a triplet it is proportional to the identity on the spin factor. Thus first-order nondegenerate perturbation theory, with this trivial diagonal treatment of spin degeneracy, gives the shifts corresponding to the three rows in part (b):These formulae also apply for $J<0$, with the reordered levels described above. At $J=0$, they resolve the fourfold $5\epsilon$ level into a shifted triplet and singlet. The next doubly occupied orbital ${\Phi }_{22}^{+}$ still has zero first-order shift. The perturbative requirement is $|\alpha |a^2\ll \epsilon$ for mixing with remote orbital states; the spin-independent perturbation does not require division by the small singlet–triplet gap.