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Title: Can molecular projected density of states (PDOS) be systematically used in electronic conductance analysis?

Abstract

Using benzenediamine and benzenedithiol molecular junctions as benchmarks, we investigate the widespread analysis of the quantum transport conductance in terms of the projected density of states (PDOS) onto molecular orbitals (MOs). We first consider two different methods for identifying the relevant MOs: (1) diagonalization of the Hamiltonian of the isolated molecule and (2) diagonalization of a submatrix of the junction Hamiltonian constructed by considering only basis elements localized on the molecule. We find that these two methods can lead to substantially different MOs and hence PDOS. Furthermore, within Method 1, the PDOS can differ depending on the isolated molecule chosen to represent the molecular junction (e.g., with or without dangling bonds); within Method 2, the PDOS depends on the chosen basis set. We show that these differences can be critical when the PDOS is used to provide a physical interpretation of the conductance (especially when its value is small, as it happens typically at zero bias). In this work, we propose a new approach in an attempt to reconcile the two traditional methods. Although some improvements were achieved, the main problems remain unsolved. Our results raise more general questions and doubts on a PDOS-based analysis of the conductance.

Authors:
 [1];  [2];  [3]
  1. Univ. Catholique de Louvain, Ottignies-Louvain-la-Neuve (Belgium). Inst. of Condensed Matter and Nanosciences. Chemin des Étoiles; European Theoretical Spectroscopy Facility (ETSF); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
  2. Univ. Catholique de Louvain, Ottignies-Louvain-la-Neuve (Belgium). Inst. of Condensed Matter and Nanosciences. Chemin des Étoiles; European Theoretical Spectroscopy Facility (ETSF)
  3. European Theoretical Spectroscopy Facility (ETSF); Centre National de la Recherche Scientifique (CNRS), Inst. Neel, Grenoble (France); Univ. Grenoble Alpes, Grenoble (France)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1628615
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Beilstein Journal of Nanotechnology
Additional Journal Information:
Journal Volume: 6; Journal ID: ISSN 2190-4286
Publisher:
Beilstein Institute
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; Science & Technology - Other Topics; Materials Science; Physics; benzene-diamine; benzene-dithiol; DFT-Landauer; molecular electronics; nanoelectronics; quantum transport

Citation Formats

Rangel, Tonatiuh, Rignanese, Gian-Marco, and Olevano, Valerio. Can molecular projected density of states (PDOS) be systematically used in electronic conductance analysis?. United States: N. p., 2015. Web. https://doi.org/10.3762/bjnano.6.128.
Rangel, Tonatiuh, Rignanese, Gian-Marco, & Olevano, Valerio. Can molecular projected density of states (PDOS) be systematically used in electronic conductance analysis?. United States. https://doi.org/10.3762/bjnano.6.128
Rangel, Tonatiuh, Rignanese, Gian-Marco, and Olevano, Valerio. Thu . "Can molecular projected density of states (PDOS) be systematically used in electronic conductance analysis?". United States. https://doi.org/10.3762/bjnano.6.128. https://www.osti.gov/servlets/purl/1628615.
@article{osti_1628615,
title = {Can molecular projected density of states (PDOS) be systematically used in electronic conductance analysis?},
author = {Rangel, Tonatiuh and Rignanese, Gian-Marco and Olevano, Valerio},
abstractNote = {Using benzenediamine and benzenedithiol molecular junctions as benchmarks, we investigate the widespread analysis of the quantum transport conductance in terms of the projected density of states (PDOS) onto molecular orbitals (MOs). We first consider two different methods for identifying the relevant MOs: (1) diagonalization of the Hamiltonian of the isolated molecule and (2) diagonalization of a submatrix of the junction Hamiltonian constructed by considering only basis elements localized on the molecule. We find that these two methods can lead to substantially different MOs and hence PDOS. Furthermore, within Method 1, the PDOS can differ depending on the isolated molecule chosen to represent the molecular junction (e.g., with or without dangling bonds); within Method 2, the PDOS depends on the chosen basis set. We show that these differences can be critical when the PDOS is used to provide a physical interpretation of the conductance (especially when its value is small, as it happens typically at zero bias). In this work, we propose a new approach in an attempt to reconcile the two traditional methods. Although some improvements were achieved, the main problems remain unsolved. Our results raise more general questions and doubts on a PDOS-based analysis of the conductance.},
doi = {10.3762/bjnano.6.128},
journal = {Beilstein Journal of Nanotechnology},
number = ,
volume = 6,
place = {United States},
year = {2015},
month = {1}
}

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    Works referencing / citing this record:

    First-principles molecular transport calculation for the benzenedithiolate molecule
    journal, October 2017