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Two distinguishable particles with equal one-particle spectra have degenerate ordered orbital products $|r,s⟩$ and $|s,r⟩$ for $r\ne s$. Suppose both individual position means vanish, as in a centred parity-symmetric well. The perturbation $\alpha x_1{x}_2$ then has zero diagonal matrix elements, but its restriction to this two-dimensional subspace isDegenerate perturbation theory gives normalized symmetric and antisymmetric eigenfunctions $(|r,s⟩\pm |s,r⟩)/\sqrt{2}$ with shifts $\pm \alpha |x_{rs}{|}^2$. Thus vanishing diagonal expectations in a chosen degenerate basis do not imply vanishing first-order energy shifts. Distinguishability permits both exchange symmetries; it does not forbid their energy splitting.

For an infinite square well of width $a$, the first two orbitals have $|x_{12}{|}^2=256a^2/(81{\pi }^4)$ by the position matrix elements in a symmetric infinite square well. If the particles are identical spin one-half fermions, the spatially symmetric and antisymmetric combinations must instead be paired with the singlet state and triplet states, respectively. A spin-independent perturbation leaves each allowed spin multiplicity intact.

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.

Use zero-based labels to agree with ${\varphi }_0$ in the later parts. The normalized infinite square well energy eigenstates and energy eigenvalues areThe position matrix elements in a symmetric infinite square well, obtained by integrating the product of the two wavefunctions against $x$, areThe integral in the question uses positive integer labels; replacing them by $k+1,n+1$ is essential here. Only opposite-parity states, $k+n$ odd, contribute, as also follows from the parity operator selection rule.

Second-order nondegenerate perturbation theory now gives the requested infinite sum:In fully explicit form this isThe symbol $m$ here denotes the electron mass, not a summation index. For the ground state $n=0$, every denominator in the first form is negative, so the ground energy level moves downward. For excited states, contributions from lower and higher energy levels have opposite signs.