Past exam of the chemistry A course of the University of Cambridge 2022 Paper 1 A5 a i Solution 2026-10-20
For a displacement group representation, an atom contributes only if the operation leaves its site fixed. Its three Cartesian displacements then contribute the trace of the polar-vector transformation.
Take perpendicular to the ring and an in-plane axis through opposite carbon atoms. To avoid confusing the principal twofold rotation with the in-plane axes, write for the former, for an in-plane axis through atoms and for one through opposite bond midpoints. The carbon displacement characters in the D6h molecular point group areA through-atom half-turn fixes two carbon sites and has Cartesian trace , giving . The molecular-plane reflection fixes all six carbons with trace , giving . A through-atom vertical mirror fixes two sites with trace , giving .
Using molecular character reduction, the 18-dimensional carbon-only result isThe six one-dimensional terms contribute six dimensions and the six copies of two-dimensional representations contribute twelve, totaling eighteen. The distinction between carbon-only and whole-molecule displacements is needed in part (ii).
For the character of a localized orbital basis, take the trace of the transformation matrix: both permutation of centres and signs of atomic orbitals matter. The two metal centres lie on the principal axis and remain fixed under rotation about . At either metal the basis has the matrixThe full four-dimensional group representation is block diagonal with two such blocks. Consequently , and for the rotation of the D6h molecular point group, .
The planar benzene structure has a sixfold principal axis normal to its plane, six transverse twofold axes, the molecular mirror plane and an inversion centre. Its molecular point group is , the D6h molecular point group.