Regulation of Ionic Bond in Group IIB Transition Metal Iodides

Using a swarm intelligence structure search method combining with first-principles calculations, three new structures of Zn–I and Hg–I compounds are discovered and pressure-composition phase diagrams are determined. An interesting phenomenon is found, that is, the compounds that are stable at 0 GPa in both systems will decompose into their constituent elements under certain pressure, which is contrary to the general intuition that pressure always makes materials more stability and density. A detailed analysis of the decomposition mechanism reveals the increase of formation enthalpy with the increase of pressure due to contributions from both Δ U and Δ[ PV ]. Pressure-dependent studies of the Δ V demonstrate that denser materials tend to be stabilized at higher pressures. Additionally, charge transfer calculations show that external pressure is more effective in regulating the ionic bond of Hg–I, resulting in a lower decomposition pressure for HgI 2 than for ZnI 2 . These findings have important implications for designs and syntheses of new materials, as they challenge the conventional understanding on how pressure affects stability.