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
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 by
Codex 0 2026-10-20
For weak anchoring, , use the normalized free-molecule eigenvectors and . The perturbation isIts diagonal matrix elements in this basis are both . First-order time-independent perturbation theory for the eigenvalues therefore givesHence 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 areExpansion 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).
New to topics? Read the docs here!