Past exam of the chemistry course of the year 3 of the natural sciences course of the University of Cambridge / 2022 / Paper 2B / Section B / 36 / a / i

The drawn $x,y$ axes pass through opposite sites, rather than along the square edges. In the D4h molecular point group class order $(E,2C_4,C_2,2C_2^{\prime },2C_2^{\prime \prime },i,2S_4,{\sigma }_h,2{\sigma }_v,2{\sigma }_d)$, an s orbital contributes $+1$ whenever its centre is fixed and zero otherwise. ThusFor example, a transverse twofold rotation about the printed $x$ axis fixes sites 1 and 3, while its diagonal counterpart exchanges all four sites. Reflection in the square plane fixes every site. Taking character inner products, with class sizes $(1,2,1,2,2,1,2,1,2,2)$, givesThese have dimensions $1+1+2=4$. The $B_{1g}$ label is tied to the printed diagonal-axis convention; rotating the transverse coordinate labels by $45^{\circ }$ would interchange $B_{1g}$ and $B_{2g}$.