Energy Level Alignment at Molecule-Metal Interfaces from an
Optimally-Tuned Range-Separated Hybrid Functional
release_o53bun46sfaujdvt5abizig65a
by
Zhenfei Liu, David A. Egger, Sivan Refaely-Abramson, Leeor Kronik, and
Jeffrey B. Neaton
2017
Abstract
The alignment of the frontier orbital energies of an adsorbed molecule with
the substrate Fermi level at metal-organic interfaces is a fundamental
observable of significant practical importance in nanoscience and beyond.
Typical density functional theory calculations, especially those using local
and semi-local functionals, often underestimate level alignment leading to
inaccurate electronic structure and charge transport properties. In this work,
we develop a new fully self-consistent predictive scheme to accurately compute
level alignment at certain classes of complex heterogeneous molecule-metal
interfaces based on optimally-tuned range-separated hybrid functionals.
Starting from a highly accurate description of the gas-phase electronic
structure, our method by construction captures important nonlocal surface
polarization effects via tuning of the long-range screened exchange in a
range-separated hybrid in a non-empirical and system-specific manner. We
implement this functional in a plane-wave code and apply it to several
physisorbed and chemisorbed molecule-metal interface systems. Our results are
in quantitative agreement with experiments, both the level alignment and work
function changes. Our approach constitutes a new practical scheme for accurate
and efficient calculations of the electronic structure of molecule-metal
interfaces.
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