Mechanisms of shear-induced solid-state reactions

Both experiments and band-structure calculations indicate that shear strains lead to closure of energy band gaps in periodic solids, and closure of the LUMO-HOMO gaps in molecules (this is also expected for non-metallic glasses). It allows athermal and ultrafast mechano-chemical reactions to occur. Simple models account for the phenomena. For periodic solids, shear shortens one axis and extends another. In contrast, hydrostatic compression causes both axes to contract. Thus the former shifts the band gaps oppositely for the two directions, causing a reduction in the minimum gap. For molecules, shear tends to increase the bonding orbitals while decreasing the antibonding orbitals, thereby reducing the LUMO-HOMO gaps. The models are consistent with band structure models for diamond. Shear-induced gap reductions account for the athermal chemical reactions observed by Bridgman, Enikolopyan, Boldyrev, and others. They account for the ultra-fast reactions that occur in explosives.