Past exam of the chemistry A course of the University of Cambridge 2022 Paper 1 A5 c iii Solution 2026-10-20
One quantum in an normal mode gives an vibrational pair. The electronic factor is , henceThis follows by multiplying the characters of the two group representations. In particular, multiplication of by produces in the hexagonal group, and the inversion parities multiply as . The resulting vibronic state is twofold degenerate.
Past exam of the chemistry A course of the University of Cambridge 2022 Paper 1 A5 c iv Solution 2026-10-20
The initial vibronic state is and the final one is , so an in-plane dipole component satisfiesThe product contains the totally symmetric representation. The combined electronic–vibrational transition is therefore symmetry-allowed, with an in-plane electric dipole transition moment.
A nonzero intensity still needs vibronic coupling. In a coordinate-independent separation, the forbidden electronic matrix element would remain zero. Its first derivative with respect to the coordinate can instead be nonzero, and the vibrational factor supplies the required one-quantum transition. This is vibrational activation of an electronic transition and explains why the band can be weak.
An otherwise forbidden electronic transition gains intensity when accompanying molecular vibration supplies a symmetry factor that permits a nonzero electric dipole transition moment. A symmetry-allowed total vibronic state specifies a possible transition, while the coupling determines its actual strength.