On the ability of periodic dispersion-corrected DFT calculations to predict molecular crystal polymorphism in para-diiodobenzene

Abstract

Periodic DFT calculations employing the PBE, PBE0 and B3LYP functionals coupled with different dispersion correction schemes have been applied to para-diiodobenzene molecular crystal in order to determine how they perform in reproducing the energetic and crystal geometry of its two well known polymorphs.Our results demonstrate that, provided that the dispersion correction scheme proposed by Tkatchenko and Scheffler [Phys. Rev. Lett. 102 (2009) 073005] is used, DFT can be successfully employed to predict the geometric structure and energy ordering of the α and β forms of para-diiodobenzene molecular crystal, with an accuracy comparable to that yielded by diffusion Monte Carlo calculations.