Solution

ID: past-exam-of-the-chemistry-course-of-the-year-3-of-the-natural-sciences-course-of-the-university-of-cambridge/2022/paper-4/59/c/solution

The first excited unperturbed level is twofold degenerate, spanned by and , with energy . The perturbation is . Both diagonal matrix elements vanish, but the off-diagonal element does not:
Diagonalizing the matrix with zero diagonal gives first-order shifts
with symmetric/antisymmetric combinations . Their order depends on the sign of ; the lower branch has shift . Applying nondegenerate perturbation theory to either product state would miss the splitting.

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