Solution

ID: past-exam-of-the-chemistry-course-of-the-year-3-of-the-natural-sciences-course-of-the-university-of-cambridge/2022/paper-2a/section-b/24/b/ii/solution

For weak anchoring, , use the normalized free-molecule eigenvectors and . The perturbation is
Its diagonal matrix elements in this basis are both . First-order time-independent perturbation theory for the eigenvalues therefore gives
Hence and . The zero free translation requires taking a square root of its new eigenvalue, rather than Taylor-expanding the frequency about zero. It is not a degenerate eigenvalue in the stipulated one-dimensional two-coordinate model.
As a check, the exact squared frequencies are
Expansion gives the same first-order results; the next lower-mode correction is . The perturbed eigenvectors contain small translation/stretch admixtures of order , consistent with the failure of uniform translation to remain an exact mode in orientation (1).

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