Converging ab initio phonon simulations for organic molecular crystals: the effect of charge density grids and phonon dispersion sampling

Abstract

We here explore how some frequently overlooked computational parameters affect the simulation of phonon frequencies in organic molecular crystals within the framework of density functional perturbation theory in a pseudo-core plane wave basis set. Specifically, we investigate how the density of the Fourier grid that is used to map real-space charge density affects the phonon frequencies and eigenvectors. We find that varying the density of this Fourier grid can affect low-frequency phonons by tens of wavenumbers and significantly alter the associated normal mode eigenvectors. Furthermore, we demonstrate that poorly converged charge density representations can lead to substantial errors in simulated thermodynamic quantities, with vibrational free energies affected by 3–4 kJ mol⁻¹ in certain systems. We show how this variation in predicted free energies can have a significant impact on our ability to correctly predict the relative stability of a series of model polymorphic systems. We finally discuss how careful convergence with respect to the Brillouin zone (q-point) sampling is imperative for the correct modelling of phonon dispersion relations in organic molecular crystals, particularly for systems characterised by weak, anisotropic interactions. Whilst no definitive ‘rules of thumb’ emerge for the convergence of these parameters, our findings highlight the critical role they play in obtaining reliable phonon frequencies from density functional perturbation theory. Our results also offer insight into the potential magnitude of errors that could arise in phonon simulations of organic molecular crystals if these parameters are not chosen carefully.