Molecule-metal interfaces are ubiquitous in nanoscale functional materials and energy-related applications. Characterizing the electronic structure at molecule-metal interfaces, especially the level alignment between molecular frontier orbitals and the Fermi level of the combined system, is crucial for understanding charge dynamics. Typical density functional theory calculations, especially when using local and semi-local functionals, often underestimate it leading to incorrect predictions of electronic structure and charge transport properties. In this work, we develop a new fully self-consistent scheme based on the optimally-tuned range-separated hybrid functional, to accurately determine the level alignment at complex heterogeneous molecule-metal interfaces. We apply this approach to several physisorbed and chemisorbed molecule-metal interface systems, which lead to quantitative agreement with reference data from experimental measurements, both for level alignments and work function changes.

Accurate level alignment at molecule-metal interfaces from an optimally-tuned range-separated hybrid functional

253rd National Meeting (2017)

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