Solution

ID: past-exam-of-the-chemistry-a-course-of-the-university-of-cambridge/2025/paper-1/a3/d/i/solution

This is a rovibrational spectrum: the vibrational excitation is accompanied by quantized molecular rotation. The high-wavenumber R branch has , and the low-wavenumber P branch has . In the simplest common- approximation,
Consecutive lines within either branch are therefore separated by roughly , while the gap between P(1) and R(0) is roughly . There is no Q branch: for this diatomic parallel transition, the electric-dipole rotational selection rule allows , and the line strength vanishes.
The intensity envelope comes from rotational populations, approximately , together with the rotational line strengths. The paired peaks arise from the two chlorine isotopologues, and : their different reduced masses shift both rotational and vibrational spacings. The more abundant gives the stronger member. The changing spacing away from the band centre reflects and, at higher , centrifugal distortion; it is not evidence for additional vibrational fundamentals.

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