Past exam of the chemistry course of the year 3 of the natural sciences course of the University of Cambridge / 2022 / Paper 2A / Section A / 14

Use the D3h molecular point group for phosphorus pentafluoride, with $z$ along the two axial P–F bonds. For each symmetry operation, only atoms left in place contribute to the character of the Cartesian displacement representation; each contributes the trace of the corresponding $3\times 3$ spatial matrix. In the class order $E,2C_3,3C_2^{\prime },{\sigma }_h,2S_3,3{\sigma }_v$ this givesFor example a $C_2^{\prime }$ fixes P and one equatorial F, and each fixed atom has Cartesian trace $-1$, giving $-2$. reflection in the equatorial plane fixes four atoms, each with trace $1$, giving $4$. Reduction with the character table givesSubtract translations $E^{\prime }+A_2^{\prime \prime }$ and rotations $A_2^{\prime }+E^{\prime \prime }$ to obtainIts dimension is $2+6+2+2=12=3(6)-6$, as required for a nonlinear six-atom molecule. Thus there are eight symmetry-distinct fundamental frequencies in the harmonic picture, with each E mode doubly degenerate. This analysis concerns vibrations about one trigonal-bipyramidal minimum; it does not treat large-amplitude rearrangements between minima.