Extended x-ray absorption fine-structure studies have been performed at the Zn K and Cd K edges for a series of solid solutions of wurtzite Zn 1−x Cd x S samples with x = 0.0, 0.1, 0.25, 0.5, 0.75, and 1.0, where the lattice parameter as a function of x evolves according to the well-known Vegard's law. In conjunction with extensive, large-scale first-principles electronic structure calculations with full geometry optimizations, these results establish that the percentage variation in the nearest-neighbor bond distances are lower by nearly an order of magnitude compared to what would be expected on the basis of lattice parameter variation, seriously undermining the chemical pressure concept. With experimental results that allow us to probe up to the third coordination shell distances, we provide a direct description of how the local structure, apparently inconsistent with the global structure, evolves very rapidly with interatomic distances to become consistent with it. We show that the basic features of this structural evolution with the composition can be visualized with nearly invariant Zn-S 4 and Cd-S 4 tetrahedral units retaining their structural integrity, while the tilts between these tetrahedral building blocks change with composition to conform to the changing lattice parameters according to the Vegard's law within a relatively short length scale. These results underline the limits of applicability of the chemical pressure concept that has been a favored tool of experimentalists to control physical properties of a large variety of condensed matter systems.

Molecular dynamics simulations were carried out to investigate the mechanical properties of silicon nanoparticles during uniaxial compression by a flat-punch indenter. We considered a large set of systems, with dimensions in the range 10 nm to 50 nm, and various shapes like cubic (perfect and blunt), spherical, truncated spherical, and Wulff-shaped, as well as two compression orientations and two temperatures. Thorough analyses of the simulations first revealed that the relation between nanoparticle size and strength, usually termed as 'smaller is stronger', is critically dependent on the nanoparticle shape, at least for the investigated size range. For instance, a significant and size-dependent strength decrease is determined for facetted Wulff-like nanoparticles, but not for cubic or spherical systems for compression along <100>. We also found that the nanoparticle shape greatly influences plasticity. Several original plasticity mechanisms are obtained, among which the nucleation of half-loop V-shaped dislocation contained in two different {111} planes, dislocations gliding in unusual {110} planes, or the nucleation of partial dislocations in shuffle {111} planes. Our investigations suggest that plasticity properties are mainly governed by the localization of shear stress build up during elastic loading, and the geometry of surfaces in contact with indenters, these two characteristics being intimately related to the nanoparticle shape.