Solution

ID: 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/23/c/ii/solution

In the totally symmetric basis, the force constant matrix reduces to
The unperturbed eigenvalues are distinct within this symmetry block, so nondegenerate perturbation theory applies even though the full unperturbed matrix has degeneracies in different symmetry sectors. The first-order shifts are both . At second order the off-diagonal matrix element gives for the lower mode and for the upper one. Therefore
In frequency form,
The corresponding eigenvectors are and . As a check, the exact squared-frequency eigenvalues are
whose expansions reproduce the perturbation theory result. The newly lifted zero frequency scales as , so expanding as an ordinary Taylor series in would be inappropriate.

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