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Energy Level Alignment at Hybridized Organic-Metal Interfaces: The Role of Many-Electron Effects

TitleEnergy Level Alignment at Hybridized Organic-Metal Interfaces: The Role of Many-Electron Effects
Publication TypeJournal Article
Year of Publication2017
AuthorsChen, Yifeng, Tamblyn Isaac, and Quek Su Ying
JournalJ. Phys. Chem. C
Date Published06/2017
Keywords1st-principles, charge-transport, circuits, conductance, gw method, nanoscale, quasi-particle energies, self-assembled monolayers, single-molecule junctions

Hybridized Molecule/metal interfaces are ubiquitous in molecular and organic devices. The energy level alignment (ELA) of frontier molecular levels relative to the metal Fermi level (E-F) is critical to the conductance and functionality of these devices. However, a clear understanding of the ELA that includes many-electron self-energy effects is lacking. Here, we investigate the many-electron effects on the ELA using state-of-the-art, benchmark GW calculations on prototypical chemisorbed molecules on Au(111), in eleven different geometries. The GW ELA is in good agreement with photoemission for monolayers of benzene diamine on Au(111). We find that in addition to static image charge screening, the frontier levels in most of these geometries are renormalized by additional screening from substrate-mediated intermolecular Coulomb interactions. For weakly chemisorbed systems, such as amines and pyridines on Au, this additional level renormalization (similar to 1.5 eV) comes solely from static screened exchange energy, allowing us to suggest computationally more tractable schemes to predict the ELA at such interfaces, However, for more strongly chemisorbed thiolate layers, dynamical effects are present. Our ab initio results constitute an important step toward the understanding and manipulation of functional molecular/organic systems for both,fundamental studies and applications.


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