Past exam of the chemistry A course of the University of Cambridge / 2023 / Paper 1 / A4 / a / iii

Choose the phase of each inward-pointing ligand sigma bond donor lobe consistently. An operation taking one donor to another then acts as a permutation on the four donor functions. For the square, label these functions $L_1,L_2,L_3,L_4$ cyclically along $+x,+y,-x,-y$. Normalized symmetry-adapted linear combinations areThus the ligand group representation is ${\Gamma }_{\sigma }=A_{1g}+B_{1g}+E_u$. Its irreducible representations allow the first two combinations to mix with the matching nickel $d$ atomic orbitals; $E_u$ instead matches nickel $p_x,p_y$.

For the tetrahedron in the vertex order specified above, takeThe three latter functions transform like $x,y,z$. Hence ${\Gamma }_{\sigma }=A_1+T_2$. These are four ligand symmetry-adapted linear combinations, rather than the five metal $d$ functions of part (ii).