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 / 23 / e

The symmetric approach preserves the C2v molecular point group with its twofold axis z and mirror planes xz and yz. The molecular ring lies in xz. Classify orbitals by reflection signs $({\sigma }_{xz},{\sigma }_{yz})$: $A_1=(+,+)$, $B_1=(+,-)$, $B_2=(-,+)$, $A_2=(-,-)$. With globally defined p-orbital phases the molecular orbital correlation diagram givesWithin either two-orbital symmetry block the lower member remains correlated with the lower product member; the non-crossing rule prevents swapping their order through an ordinary same-symmetry crossing. Crossings between different irreducible representations are allowed. The crucial consequence is that the occupied carbon pi orbital correlates to a C–O-antibonding combination, rather than both initially occupied $A_1$ orbitals becoming the two product bonding orbitals.