Science on low-dimensional materials has been focusing on the controlled assembly of various 2D materials to generate structures with new quantum characteristics. Such modifications can be achieved by proximity effects, e.g., by intercalation and adsorption. One promising route is to use epitaxial buffer layer structures on SiC(0001) surfaces, which transform into a quasi free-standing monolayer graphene with new 2D interface structures upon intercalation. As suggested by density functional theory (DFT) studies, elements of the IV group such as Pb can be used for this purpose. In the present contribution we present DFT modeling to investigate the intercalation of buffer layers on SiC(0001) by group IV elements and their influence on the structural and electronic properties. E.g. in the case of suspended and charge neutral graphene intercalated Pb may form plumbene honeycomb lattices, which are rotated by ±7.5 degrees with respect to graphene. Along with this twist, a proximity-induced modulation of the hopping parameter in graphene opens a band gap of around 30 meV at the Fermi energy, giving rise to a metal-insulator transition. Combining those quantum mechanical simulations with optical ray tracing and a corresponding phase-space analysis shows how the distinct dwell tim