Negative thermal expansion of Cu2O studied by quasi-harmonic approximation and cubic force-constant method

Cubic cuprous oxide, Cu2O, is characterized by a peculiar structural response to temperature: it shows a relatively large negative thermal expansion below 250 K, then followed by a positive thermal expansion at higher temperatures. The two branches of its thermal expansion (negative and positive) are almost perfectly symmetric at low temperatures, with the minimum of its lattice parameter at about 250 K and with the lattice parameter at 500 K almost coinciding with that at 0 K. We perform lattice-dynamical quantum-mechanical calculations to investigate the thermal expansion of Cu2O. Phonon mode-specific Gruneisen parameters are computed, which allows us to identify different spectral regions of atomic vibrations responsible for the two distinct regimes of thermal expansion. Two different computational approaches are explored, their results compared, and their numerical aspects critically assessed: a well-established method based on the quasiharmonic approximation, where harmonic frequencies are computed at different lattice volumes, and an alternative approach, where quadratic and cubic interatomic force-constants are computed at a single volume. The latter scheme has only recently become computationally feasible in the context of lattice thermal conductivity simulations. When proper numerical parameters are used (phonon sampling, tolerances, etc.), the two approaches are here shown to provide a very consistent description, yet at a rather different computational cost. All of the experimentally observed features of the complex thermal expansion of Cu2O are correctly reproduced up to 500 K, with a slight overall underestimation of the volume contraction.Cubic cuprous oxide, Cu2O, is characterized by a peculiar structural response to temperature: it shows a relatively large negative thermal expansion below 250 K, then followed by a positive thermal expansion at higher temperatures. The two branches of its thermal expansion (negative and positive) are almost perfectly symmetric at low temperatures, with the minimum of its lattice parameter at about 250 K and with the lattice parameter at 500 K almost coinciding with that at 0 K. We perform lattice-dynamical quantum-mechanical calculations to investigate the thermal expansion of Cu2O. Phonon mode-specific Gruneisen parameters are computed, which allows us to identify different spectral regions of atomic vibrations responsible for the two distinct regimes of thermal expansion. Two different computational approaches are explored, their results compared, and their numerical aspects critically assessed: a well-established method based on the quasiharmonic approximation, where harmonic frequencies are computed a...