Between Harmonic Crystal and Glass: Solids with Dimpled Potential-Energy Surfaces Having Multiple Local Energy Minima

Solids with dimpled potential-energy surfaces are ubiquitous in nature and, typically, exhibit structural (elastic or phonon) instabilities. Dimpled potentials are not harmonic; thus, the conventional quasiharmonic approximation at finite temperatures fails to describe anharmonic vibrations in such solids. At sufficiently high temperatures, their crystal structure is stabilized by entropy; in this phase, a diffraction pattern of a periodic crystal is combined with vibrational properties of a phonon glass. As temperature is lowered, the solid undergoes a symmetry-breaking transition and transforms into a lower-symmetry phase with lower lattice entropy. Here, we identify specific features in the potential-energy surface that lead to such polymorphic behavior; we establish reliable estimates for the relative energies and temperatures associated with the anharmonic vibrations and the solid-solid symmetry-breaking phase transitions. We show that computational phonon methods can be applied to address anharmonic vibrations in a polymorphic solid at fixed temperature. To illustrate the ubiquity of this class of materials, we present a range of examples (elemental metals, a shape-memory alloy, and a layered charge-density-wave system); we show that our theoretical predictions compare well with known experimental data.

Automated summary

This study identifies specific features in the potential-energy surface that lead to polymorphic behavior and establishes reliable estimates for the relative energies and temperatures associated with anharmonic vibrations and solid-solid symmetry-breaking phase transitions. Computational phonon methods are shown to be applicable in investigating anharmonic vibrations in polymorphic solids at fixed temperatures. The theoretical predictions are well supported by a range of examples and known experimental data.