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.

Chaotic Dynamics in a Quantum Fermi–Pasta–Ulam Problem

We investigate the emergence of chaotic dynamics in a quantum Fermi—Pasta—Ulam problem for anharmonic vibrations in atomic chains applying semi-quantitative analysis of resonant interactions complemented by exact diagonalization numerical studies. The crossover energy separating chaotic high energy phase and localized (integrable) low energy phase is estimated. It decreases inversely proportionally to the number of atoms until approaching the quantum regime where this dependence saturates. The chaotic behavior appears at lower energies in systems with free or fixed ends boundary conditions compared to periodic systems. The applications of the theory to realistic molecules are discussed.