Origin of the low compressibility in hard nitride spinels -: art. no. 064115

A microscopic investigation of first-principles electron densities of gamma-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 gamma-C3N4 and different degrees of ionic polarization in gamma-Si3N4 and gamma-Ge3N4, (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.