Calculations of electrostatic potential. The present IFFT images presumably represent the interlayer moiré potential in our incommensurate and commensurate hBN layers. However, additional theoretical support would be necessary to confirm this argument. In theoretical studies of 2D materials, two models are usually employed, i.e., a periodic model and a finite model. The periodic model is based on Blochʼs theorem and utilizes periodic boundary conditions to replicate the elementary cell. This approach is in principle applicable only to commensurate systems where the momentum is well defined. In the finite model approach, one performs, for example, quantum chemical calculations using a large enough finite cluster models, whose external dangling bonds are terminated usually by hydrogen atoms. Although the results of the finite models may suffer from edge effects, this approach can be applied both to commensurate and incommensurate systems and is useful for calculating electrostatic potential (ESP) in real space. Thus, in this work, we carried out a series of quantum chemical density functional theory (DFT) calculations using sufficiently large clusters of atoms modeling the hBN bilayers with different twist angles as well as the one with the untwisted AAstacking configuration (θ = 0°). Although the DFT cal-culations were performed on several model clusters with different sizes using various density functionals under the rigid lattice approximation, we only show the results on the (B111N111H42)2 cluster at the B97XD/6-31G(d) level, as explained in 'Computational details' section in the Supporting Information.