Electronic energy level alignment at metal-molecule interfaces with a GW approach

Abstract

Using density functional theory and many-body perturbation theory within a GW approximation, we calculate the electronic structure of a metal-molecule interface consisting of benzene diamine (BDA) adsorbed on Au(111). Through direct comparison with photoemission data, we show that a conventional G${}_0$W${}_0$ approach can underestimate the energy of the adsorbed molecular resonance relative to the Au Fermi level by up to 0.8 eV. The source of this discrepancy is twofold: a 0.7 eV underestimate of the gas phase ionization energy (IE), and a 0.2 eV overestimate of the Au work function. Refinements to self-energy calculations within the GW framework that account for deviations in both the Au work function and BDA gas-phase IE can result in an interfacial electronic level alignment in quantitative agreement with experiment.

References in corpus (6)

• Renormalization of Molecular Electronic Levels at Metal-Molecule Interfaces
• First-principles GW calculations for fullerenes, porphyrins, phtalocyanine, and other molecules of interest for organic photovoltaic applications
• Renormalization of Molecular Quasiparticle Levels at Metal-Molecule Interfaces: Trends Across Binding Regimes
• Band Offsets at the Si/SiO${}_2$ Interface from Many-Body Perturbation Theory
• Relating Energy Level Alignment and Amine-Linked Single Molecule Junction Conductance
• Anomalous molecular orbital variation upon adsorption on wide band gap insulator

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