Evaluating Computational Shortcuts in Supercell-Based Phonon Calculations of Molecular Crystals: The Instructive Case...

Phonons crucially impact a variety of properties of organic semiconductor materials. For instance, charge- and heat transport depend on low-frequency phonons, while for other properties, such as the free energy, especially high-frequency phonons count. For all these quantities one needs to know the entire phonon band structure, whose simulation becomes exceedingly expensive for more complex systems when using methods like dispersion-corrected density functional theory (DFT). Therefore, in the present contribution we evaluate the performance of more approximate methodologies, including density functional tight binding (DFTB) and a pool of force fields (FF) of varying complexity and sophistication. Beyond merely comparing phonon band structures, we also critically evaluate to what extent derived quantities, like temperature-dependent heat capacities, mean squared thermal displacements, and temperature-dependent free energies are impacted by shortcomings in the description of the phonon bands. As a benchmark system, we choose (deuterated) naphthalene, as the only organic semiconductor material for which to date experimental phonon band structures are available in the literature. Overall, the best performance among the approximate methodologies is observed for a system-specifically parametrized second-generation force field. Interestingly, in the low-frequency regime also force fields with a rather simplistic model for the bonding interactions (like the General Amber Force Field) perform rather well. As far as the tested DFTB parametrization is concerned, we obtain a significant underestimation of the unit-cell volume resulting in a pronounced overestimation of the phonon energies in the low-frequency region. This cannot be mended by relying on the DFT-calculated unit cell, since with this unit cell the DFTB phonon frequencies significantly underestimate the experiments.