Transferable classical force field for pure and mixed metal halide perovskites parameterized from first principles

TL;DR

This paper develops a transferable classical force field for mixed hybrid perovskites, enabling long-time scale simulations of ion dynamics and structural properties with first-principles accuracy.

Contribution

The authors introduce a novel, transferable force field for mixed perovskites, fitted to DFT data, allowing realistic large-scale molecular dynamics simulations.

Findings

Accurately reproduces XRD patterns and lattice expansion

Provides ion diffusion coefficients from long-time MD simulations

Estimates upper limits of ion migration in photovoltaic perovskites

Abstract

Many key features in photovoltaic perovskites occur in relatively long time scales and involve mixed compositions. This requires realistic but also numerically simple models. In this work we present a transferable classical force field to describe the mixed hybrid perovskite MA$_x$FA$_{1-x}$Pb(Br$_y$I$_{1-y}$)$_3$ for variable composition ($\forall x,y \in [0,1]$). The model includes Lennard-Jones and Buckingham potentials to describe the interactions between the atoms of the inorganic lattice and the organic molecule, and the AMBER model to describe intramolecular atomic interactions. Most of the parameters of the force field have been obtained by means of a genetic algorithm previously developed to parameterize the CsPb(Br$_x$I$_{1-x}$)$_3$ perovskite. The algorithm finds the best parameter set that simultaneously fits the DFT energies obtained for several crystalline structures with moderate degrees of distortion with respect to the equilibrium configuration. The resulting model reproduces correctly the XRD patterns, the expansion of the lattice upon I/Br substitution and the thermal expansion coefficients. We use the model to run classical molecular dynamics simulations with up to 8600 atoms and simulation times of up to 40~ns. From the simulations we have extracted the ion diffusion coefficient of the pure and mixed perovskites, presenting for the first time these values obtained by a fully dynamical method using a transferable model fitted to first principles calculations. The values here reported can be considered as the theoretical upper limit for ion migration dynamics induced by halide vacancies in photovoltaic perovskite devices under operational conditions.