Energy Level Alignment at Hybridized Organic-metal Interfaces: the Role of Many-electron Effects

Abstract

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 (EF) 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 (~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 towards the understanding and manipulation of functional molecular/organic systems for both fundamental studies and applications.

arXiv commentmain text - first 22 pages

References in corpus (18)

• Van der Waals Density Functional for General Geometries
• Van der Waals density functionals applied to solids
• The GW method
• BerkeleyGW: A Massively Parallel Computer Package for the Calculation of the Quasiparticle and Optical Properties of Materials and Nanostructures
• Renormalization of Molecular Electronic Levels at Metal-Molecule Interfaces
• Single-Molecule Circuits with Well-Defined Molecular Conductance
• Mechanically-Controlled Binary Conductance Switching of a Single-Molecule Junction
• Amine-Gold Linked Single-Molecule Junctions: Experiment and Theory
• Truncation of Periodic Image Interactions for Confined Systems
• Polarization-induced renormalization of molecular levels at metallic and semiconducting surfaces
• Renormalization of Molecular Quasiparticle Levels at Metal-Molecule Interfaces: Trends Across Binding Regimes
• Coulomb-hole summations and energies for GW calculations with limited number of empty orbitals: a modified static remainder approach
• Influence of Functional Groups on Charge Transport in Molecular Junctions
• Relating Energy Level Alignment and Amine-Linked Single Molecule Junction Conductance
• Electronic energy level alignment at metal-molecule interfaces with a GW approach
• Quantitative Molecular Orbital Energies within a $G_0{W}_0$ Approximation
• Band Alignment in Molecular Devices: Influence of Anchoring Group and Metal Work Function
• Competing thermodynamic and dynamic factors select molecular assemblies on a gold surface

Cited by in corpus (7)

• Accelerating $GW$-Based Energy Level Alignment Calculations for Molecule-Metal Interfaces Using a Substrate Screening Approach
• Quasiparticle Levels at Large Interface Systems from Many-body Perturbation Theory: the XAF-GW method
• Quasiparticle electronic structure of phthalocyanine:TMD interfaces from first-principles $GW$
• Dielectric embedding GW for weakly coupled molecule-metal interfaces
• Layer-dependent Quasiparticle Electronic Structure of the P3HT:PCBM Interface from A First-Principles Substrate Screening $GW$ Approach
• Quasiparticle Electronic Structure of Two-Dimensional Heterotriangulene-Based Covalent Organic Frameworks Adsorbed on Au(111)
• A Three-Tiered Hierarchical Computational Framework Bridging Molecular Systems and Junction-Level Charge Transport