X-ray diffraction data taken at the beamtime ES-916, and for studies on AgI and SiO2

External mechanical stress alters the nature of chemical bonds and triggers novel reactions, providing interesting synthetic protocols to supplement traditional solvent- or thermo-based chemical approaches. The mechanisms of mechanochemistry have been well studied in organic materials made of a carbon-centered polymeric framework and covalence force field. They convert stress into anisotropic strain which will engineer the length and strength of targeted chemical bonds. Here, we show that by compressing silver iodide in a diamond anvil cell, the external mechanical stress weakens the Ag−I ionic bonds and activate the global diffusion of super-ions. In contrast to conventional mechanochemistry, mechanical stress imposes unbiased influence on the ionicity of chemical bonds in this archetypal inorganic salt. Our combined synchrotron X-ray diffraction experiment and first-principles calculation demonstrate that upon the critical point of ionicity, the strong ionic Ag−I bonds break down, leading to the recovery of elemental solids from a decomposition reaction. Instead of densification, our results reveal the mechanism of an unexpected decomposition reaction through hydrostatic compression and suggest the sophisticated chemistry of simple inorganic compounds under extreme conditions.