Solution

ID: past-exam-of-the-chemistry-a-course-of-the-university-of-cambridge/2024/paper-1/a4/c/i/solution

Ideal gaseous phosphorus pentachloride is a trigonal bipyramid with D3h molecular point group symmetry. There are five chlorine sites and three 3p orbitals per site, hence a fifteen-dimensional basis. A moved atom contributes zero to the character; each fixed chlorine contributes the trace of the three-dimensional polar-vector matrix acting on its local p orbitals.
For example, a axis through one equatorial chlorine fixes that site but rotates its p-vector basis with trace . Counting that atom as would be incorrect.
Apply molecular character reduction with class sizes and group order twelve:
For , this gives ; for , . The full result is
The dimension check is . As an additional transparent separation, the two axial chlorines supply , while the three equatorial ones supply . These are all chlorine 3p orbitals, including both radial and tangential functions; a five-orbital ligand-sigma basis would answer a different question.

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