Past exam of the chemistry course of the year 1 of the natural sciences course of the University of Cambridge / 2025 / 6 / b / i

Gallium phosphide forms a tetrahedral network of polar covalent bonds, with electron density displaced toward phosphorus. The alternating diamond-related structure is the zinc blende structure: each Ga has four P neighbours and each P has four Ga neighbours. A local orbital hybridization picture combines outward-pointing s,p-derived orbitals into four approximately $s{p}^3$ bond directions; in the crystal these interactions form extended occupied bonding bands.

Since ${\chi }_{\mathrm{Allen}}(\mathrm{P})-{\chi }_{\mathrm{Allen}}(\mathrm{Ga})=2.25-1.76=0.49>0$, P attracts shared electron density more strongly. Write ${\mathrm{Ga}}^{\delta +}-{\mathrm{P}}^{\delta -}$ to indicate an ionic contribution superposed on covalent bonds. Formal oxidation states Ga($+3$) and P($-3$) are electron-assignment labels, not proof of completely transferred charges or a purely ionic crystal.

Neither atom requires $3d$ hybrids for these four bonds. The Ga $3d^{10}$ shell is filled and relatively core-like; the relevant Ga valence orbitals are $4s,4p$. P uses principally $3s,3p$; its empty $3d$ orbitals are too high in energy to be a necessary bonding set. Detailed band calculations may include d-state mixing or core–valence effects, but that does not turn the tetrahedral bonding into an expanded-valence d-hybrid construction.