Solution

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

A vibrational fundamental is the transition . A first vibrational overtone is . A hot band starts from a thermally populated vibrationally excited level, such as .
For a strictly harmonic potential and a dipole linear in displacement, the allowed transitions have . A fundamental and a hot band then share the same frequency, while the overtone has zero intensity. Anharmonicity separates the adjacent gaps and can give overtone intensity; nonlinear displacement dependence of the dipole can also contribute. A hot band is defined by its lower state, not merely by being weak.

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