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Electronic level alignment at a metal-molecule interface from a short-range hybrid functional

From National Research Council Canada

DOIResolve DOI: https://doi.org/10.1063/1.3655357
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FormatText, Article
Abstract
Hybrid functionals often exhibit a marked improvement over semi-local functionals in the description of the electronic structure of organic materials. Because short-range hybrid functionals, notably the Heyd-Scuseria-Ernzerhof (HSE) functional, can also describe the electronic structure of metals reasonably well, it is interesting to examine to which extent they can correctly describe the electronic structure at metal-organic interfaces. Here, we address this question by comparing HSE calculations with many-body perturbation theory calculations in the GW approximation, or with experimental photoemission data, for two prototypical systems: benzene on graphite and benzene diamine on gold. For both cases, we find that while HSE yields results that are somewhat closer to experiment than those of semi-local functionals, the HSE prediction is still lacking quantitatively by ∼1 eV. We show that this quantitative failure arises because HSE does not correctly capture the fundamental gap of the organic or its renormalization by the metal. These discrepancies are traced back to missing long-range exchange and correlation components, an explanation which applies to any conventional or short-range hybrid functional.
Publication date
PublisherAIP Publishing
In
  • The Journal of Chemical Physics 135, no. 16, 164706.
LanguageEnglish
Peer reviewedYes
NRC publication
This is a non-NRC publication

"Non-NRC publications" are publications authored by NRC employees prior to their employment by NRC.

NPARC number23003164
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Record identifier54ad8543-d19a-4ef7-bd25-3a6c62f0c69d
Record created2018-05-03
Record modified2020-04-21
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