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A microscopic investigation of first-principles electron densities of γ-A 3 N 4 (A:C,Si,Ge) spinels reveals a clear relationship between the compressibility and the chemical bonding of these materials. Three striking findings emanate from this analysis: (i) the chemical graph is governed by a network of highly directional strong bonds with covalent character in γ-C 3 N 4 and different degrees of ionic polarization in γ-Si 3 N 4 and γ-Ge 3 N 4 , (ii) nitrogen is the lowest compressible atom controlling the trend in the bulk modulus of the solids. and (iii) the group-IV counterions show strong site dependent compressibilities enhancing the difficulty in the synthesis of the spinel phases of these nitrides.

Origin of the low compressibility in hard nitride spinels