We use a combination of density functional theory (DFT) and dynamical mean field theory (DMFT) to unveil orbital field-induced electronic structure reconstruction of the atomic Sn layer deposited onto a Si (111) surface (Sn/Si (111)− 3× 3 R 30∘), also referred to as α-Sn. Our DFT+ DMFT results indicate that α-Sn is an ideal testing ground to explore electric field-driven orbital selectivity and Mott memory behavior, all arising from the close proximity of α-Sn to metal insulator transitions. We discuss the relevance of orbital phase changes for α-Sn in the context of the current–voltage (I− V) characteristic for future silicon-based metal semiconductor atomristors.