Unmasking Charge Transfer in the Misfits: ARPES and <i>Ab Initio</i> Prediction of Electronic Structure in Layered Incommensurate Systems without Artificial Strain

Common belief is that the large band shifts observed in incommensurate misfit compounds, e.g., (LaSe)_{1.14}(NbSe_{2})_{2}, are due to interlayer charge transfer. By contrast, our analysis, based on both angle-resolved photoemission spectroscopy (ARPES) measurements and a specialized ab initio framework employing only quantities well defined in incommensurate materials, demonstrates that the large band shifts instead reflect changes in valence band hybridization and interlayer bonding. The strong alignment of our ab initio predictions and ARPES measurements confirms our understanding of the incommensurate electronic structure and charge transfer.