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Title: Energy level alignment at molecule-metal interfaces from an optimally tuned range-separated hybrid functional

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. Here, 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, the both the level alignment and work function changes. This approach constitutes a new practical scheme for accurate and efficient calculations of the electronic structure of molecule-metal interfaces.

Authors:
 [1];  [2];  [2];  [2];  [3]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry and Materials Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Physics
  2. Weizmann Inst. of Science, Rehovot (Israel). Dept. of Materials and Interfaces
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry and Materials Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Physics; Kavli Energy Nanosciences Inst., Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1379765
Alternate Identifier(s):
OSTI ID: 1349135
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 9; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Liu, Zhen-Fei, Egger, David A., Refaely-Abramson, Sivan, Kronik, Leeor, and Neaton, Jeffrey B. Energy level alignment at molecule-metal interfaces from an optimally tuned range-separated hybrid functional. United States: N. p., 2017. Web. doi:10.1063/1.4975321.
Liu, Zhen-Fei, Egger, David A., Refaely-Abramson, Sivan, Kronik, Leeor, & Neaton, Jeffrey B. Energy level alignment at molecule-metal interfaces from an optimally tuned range-separated hybrid functional. United States. doi:10.1063/1.4975321.
Liu, Zhen-Fei, Egger, David A., Refaely-Abramson, Sivan, Kronik, Leeor, and Neaton, Jeffrey B. Tue . "Energy level alignment at molecule-metal interfaces from an optimally tuned range-separated hybrid functional". United States. doi:10.1063/1.4975321. https://www.osti.gov/servlets/purl/1379765.
@article{osti_1379765,
title = {Energy level alignment at molecule-metal interfaces from an optimally tuned range-separated hybrid functional},
author = {Liu, Zhen-Fei and Egger, David A. and Refaely-Abramson, Sivan and Kronik, Leeor and Neaton, Jeffrey B.},
abstractNote = {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. Here, 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, the both the level alignment and work function changes. This approach constitutes a new practical scheme for accurate and efficient calculations of the electronic structure of molecule-metal interfaces.},
doi = {10.1063/1.4975321},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 9,
volume = 146,
place = {United States},
year = {2017},
month = {2}
}

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