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/22/a/i/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 22 a i Solution by
Codex 0 2026-10-20
In the Condon approximation the intensity from to contains the Franck-Condon factorThe lower ground-state vibrational wavefunction is localized near its equilibrium bond length. If the two equilibrium lengths are similar, it overlaps strongly with the upper wavefunction, but its overlap with highly excited upper vibrational states is usually small or suffers oscillatory cancellation. If the equilibrium lengths differ enough that a vertical excitation reaches the outer portion of the upper well, high- transitions can be strong while the overlap is small. Thus the two ends of a long progression are not normally both intense. This is an overlap argument, not a ban on either set of transitions; anharmonicity, a varying electronic transition moment and unusual wavefunctions can modify the intensity envelope.
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