Failure of Conventional Density Functionals for the Prediction of Molecular Crystal Polymorphism: A Quantum Monte Carlo Study

Abstract

We have applied the diffusion Monte Carlo method, for the first time, to an organic molecular crystal (para-diiodobenzene) in order to determine the relative stability of its two well-known polymorphs. The DMC result predicts that the α phase is more stable than the β phase at zero temperature, in agreement with experiment. In comparison, we evaluated four commonly used local, semilocal, and hybrid density functionals, including an empirical correction to include the effects of dispersion. We conclude that while density functional theory may provide the most practical method for estimating the effects of electron correlation, conventional functionals which do not accurately describe noncovalent interactions may not be considered reliable for determining highly accurate energies in such systems.