Rationalizing polymorphism with local correlation-based methods: a case study of pnictogen molecular crystals.

Abstract

A computational workflow is proposed to quantify and rationalize the relative stability of different structures of molecular crystals using cluster models and quantum chemical methods. The Hartree-Fock plus London Dispersion (HFLD) scheme is used to estimate the lattice energy of molecular crystals in various structural arrangements. The fragment-pairwise Local Energy Decomposition (fp-LED) scheme is then employed to quantify the key intermolecular interactions responsible for the relative stability of different crystal structures. The fp-LED scheme provides also in-depth chemical insights by decomposing each interaction into energy components such as dispersion, electrostatics, and exchange. Notably, this analysis requires only a single interaction energy computation per structure on a suitable cluster model. As a case study, two polymorphs of each of the following are considered: naphthyl-substituted dipnictanes (with As, Sb, and Bi as the pnictogen atom) and tris(thiophen-2-yl)bismuthane. The approach outlined offers high accuracy as well as valuable insights for developing design principles to engineer crystal structures with tailored properties, opening up new avenues in the study of molecular aggregates, potentially impacting diverse fields in materials science and beyond.