Solution

ID: past-exam-of-the-chemistry-a-course-of-the-university-of-cambridge/2024/paper-1/a3/a/ii/solution

The two extra progressions are rotational transitions within thermally populated and vibrational levels. Isotopic purity rules out attributing them to different isotope masses. Their rotational constants are
The Boltzmann distribution makes each higher vibrational manifold less populated, so its rotational spectrum is weaker. A Morse oscillator explores larger separations as it is excited: the bond's vibrationally averaged moment of inertia increases and the rotational spacing decreases. More precisely, involves an average of the inverse square separation; it is not simply the inverse square of the mean separation.
The observed decrement is constant to the given precision:
This fits the leading vibration-rotation interaction law .

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