Effective dynamic constants for nonequilibrium third-principles simulations

Abstract

Computational studies of the thermodynamic properties of materials at the mesoscopic and macroscopic scales -- involving lengths and times of at least $\mu$m and $\mu$s, respectively -- rely on a coarse-graining approximation such that only a few relevant collective variables are treated explicitly. Those variables typically take the form of fields defined everywhere in space or macroscopic quantities when spatial inhomogeneities can be treated implicitly. The free energy is usually expressed as a Landau-like potential whose temperature-dependent minima track stable states, characteristic equilibrium fluctuations being implicitly accounted for. Further, the response of the system to external perturbations, and its relaxation toward thermal equilibrium, are described in terms of simple equations of motion governed by effective inertial and viscous-damping constants. There is considerable literature on the problem of deriving Landau free energy potentials, from either experiment or predictive atomistic simulations, including recent efforts to develop systematic machine-learning approaches that we denote ``third principles''. Much less attention has received the calculation of the effective constants controlling the nonequilibrium macroscopic or mesoscopic dynamics. Here we tackle that problem, describing a protocol that allows us to compute the temperature-dependent inertial and damping coefficients associated to the electric polarization in representative soft-mode ferroelectric PbTiO$_{3}$. Our scheme lends itself to a widespread application, although the non-trivial behaviors found in PbTiO$_{3}$ suggest that more case studies will be needed to finetune a general and robust calculation protocol. Our results also allow us to comment on common assumptions in the literature of effective dynamic treatments of ferroelectrics and related materials.