We report a density functional theory (DFT) study of ${\mathrm{Ag}}_3\mathrm{Co}\left(\mathrm{CN}\right){}_6$, a material noted for its colossal positive and negative thermal expansion, and its giant negative linear compressibility. Here, we explicitly include the dispersive interaction within the DFT calculation, and find that it is essential to reproduce the ground state, the high-pressure phase, and the phonons of this material, and hence essential to understand this material's remarkable physical properties. New exotic properties are predicted. These include heat enhancement of the negative linear compressibility, a large reduction in the coefficient of thermal expansion on compression with change of sign of the mode Grüneisen parameters under pressure, and large softening of the material on heating. Our results suggest that these are associated with the weak Ag–Ag dispersive interactions acting with an efficient hinging mechanism in the framework structure.

• Received 13 June 2014
• Revised 31 July 2014

DOI:https://doi.org/10.1103/PhysRevB.90.054302