Systematic DFT Modeling van der Waals Heterostructures from a Complete Configurational Basis Applied to γ-PC/WS 2 .

Periodic boundary conditions in density functional theory (DFT)-based modeling of bilayer van der Waals heterostructures introduce an artificial lock to a metastable configuration. Depending on the initial supercell, geometric optimization may reach local energy minima at a fixed twist-angle in a restricted strain-space. In this work, an algorithm was introduced for generating a complete scope of ways to combine two monolayer unit cells into a common supercell. In its application to γ-PC/WS ₂ , 18,123 bilayer supercells were derived, for which the constituting monolayers possessed isotropic strains, anisotropic strains, or intralayer shear strains. Based on analysis, 45 isotropically strained configurations were carefully chosen for optimization by DFT. Geometric and energetic features and band structures were revealed and compared, following the variations at different strains and twist-angles. As such, this case study brought to resolution the impacts of supercell construction on DFT's outcomes and the merits of in-depth screening of the different options. Repetitions and extensions to the demonstrated approach may be applied to characterize van der Waals heterostructures and derivatives in the future.