Title: Second order structural phase transitions, free energy curvature, and temperature-dependent anharmonic phonons in the self-consistent harmonic approximation: theory and stochastic implementation,
Abstract: The self-consistent harmonic approximation is an effective harmonic theory to
calculate the free energy of systems with strongly anharmonic atomic
vibrations, and its stochastic implementation has proved to be an efficient
method to study, from first-principles, the anharmonic properties of solids.
The free energy as a function of average atomic positions (centroids) can be
used to study quantum or thermal lattice instability. In particular the
centroids are order parameters in second-order structural phase transitions
such as, e.g., charge-density-waves or ferroelectric instabilities. According
to Landau's theory, the knowledge of the second derivative of the free energy
(i.e. the curvature) with respect to the centroids in a high-symmetry
configuration allows the identification of the phase-transition and of the
instability modes. In this work we derive the exact analytic formula for the
second derivative of the free energy in the self-consistent harmonic
approximation for a generic atomic configuration. The analytic derivative is
expressed in terms of the atomic displacements and forces in a form that can be
evaluated by a stochastic technique using importance sampling. Our approach is
particularly suitable for applications based on first-principles
density-functional-theory calculations, where the forces on atoms can be
obtained with a negligible computational effort compared to total energy
determination. Finally we propose a dynamical extension of the theory to
calculate spectral properties of strongly anharmonic phonons, as probed by
inelastic scattering processes. We illustrate our method with a numerical
application on a toy model that mimics the ferroelectric transition in
rock-salt crystals such as SnTe or GeTe.