Localized π Surface States on 2D Molybdenum Disulfide from Carbene-Functionalization as a Qubit Design Strategy

[Image: see text] Surface chemistry is increasingly important for a number of applications, from catalysis to molecular qubits. For the qubit application, it is imperative that the energy levels of surface species involved in the process of interest are energetically distinct—that is addressable and not buried below or coincident with the substrate energy levels. One way to afford this is through chemical functionalization with derivatives that impart the property of choice to the interface. In this Letter, we report on the nature of the bond between a carbene moiety and an MoS(2) surface. With density functional theory (DFT) and spin-polarized calculations, we first observe states in the band structure that pertain to the carbene group and then prove their origin. Importantly, we find localized π-states in the band gap that are due to π-electrons that are part of a diene attached to the carbene carbon and are not available in bonding configurations without the π conjugation. These lead to open-shell monocationic structures involving midgap HOMOs with densities on the carbene moiety. Both neutral and cationic forms of the carbenes are energetically separate from the MoS(2) substrate, thus useful for optical manipulation. We explore several different choices of the carbene moieties, and show that those based on fused thiophene and bithiophene structures are the most favorable for localization, while purely carbon-based aromatic structures lead to states that are delocalized onto the MoS(2) and thus less useful. These findings are potentially of interest to the design and synthesis of future molecular qubit candidates for device fabrication.