Electrode-molecule energy level offsets in a gold-benzene diamine-gold single molecule tunnel junction

One means for describing electron transport across single molecule tunnel junctions (MTJs) is to use density functional theory (DFT) in conjunction with a nonequilibrium Green's function formalism. This description relies on interpreting solutions to the Kohn-Sham (KS) equations used to solve t...

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Main Authors: Szepieniec, Mark S., Greer, James C.
Format: Article
Language:English
Published: American Institute of Physics Inc. 2020
Subjects:
Online Access:https://eprints.nottingham.ac.uk/63914/
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author Szepieniec, Mark S.
Greer, James C.
author_facet Szepieniec, Mark S.
Greer, James C.
author_sort Szepieniec, Mark S.
building Nottingham Research Data Repository
collection Online Access
description One means for describing electron transport across single molecule tunnel junctions (MTJs) is to use density functional theory (DFT) in conjunction with a nonequilibrium Green's function formalism. This description relies on interpreting solutions to the Kohn-Sham (KS) equations used to solve the DFT problem as quasiparticle (QP) states. Many practical DFT implementations suffer from electron self-interaction errors and an inability to treat charge image potentials for molecules near metal surfaces. For MTJs, the overall effect of these errors is typically manifested as an overestimation of electronic currents. Correcting KS energies for self-interaction and image potential errors results in MTJ current-voltage characteristics in close agreement with measured currents. An alternative transport approach foregoes a QP picture and solves for a many-electron wavefunction on the MTJ subject to open system boundary conditions. It is demonstrated that this many-electron method provides similar results to the corrected QP picture for electronic current. The analysis of these two distinct approaches is related through corrections to a junction's electronic structure beyond the KS energies for the case of a benzene diamine molecule bonded between two gold electrodes.
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spelling nottingham-639142020-12-03T06:00:32Z https://eprints.nottingham.ac.uk/63914/ Electrode-molecule energy level offsets in a gold-benzene diamine-gold single molecule tunnel junction Szepieniec, Mark S. Greer, James C. One means for describing electron transport across single molecule tunnel junctions (MTJs) is to use density functional theory (DFT) in conjunction with a nonequilibrium Green's function formalism. This description relies on interpreting solutions to the Kohn-Sham (KS) equations used to solve the DFT problem as quasiparticle (QP) states. Many practical DFT implementations suffer from electron self-interaction errors and an inability to treat charge image potentials for molecules near metal surfaces. For MTJs, the overall effect of these errors is typically manifested as an overestimation of electronic currents. Correcting KS energies for self-interaction and image potential errors results in MTJ current-voltage characteristics in close agreement with measured currents. An alternative transport approach foregoes a QP picture and solves for a many-electron wavefunction on the MTJ subject to open system boundary conditions. It is demonstrated that this many-electron method provides similar results to the corrected QP picture for electronic current. The analysis of these two distinct approaches is related through corrections to a junction's electronic structure beyond the KS energies for the case of a benzene diamine molecule bonded between two gold electrodes. American Institute of Physics Inc. 2020-11-02 Article PeerReviewed application/pdf en cc_by https://eprints.nottingham.ac.uk/63914/1/Electrode-molecule%20energy%20level%20offsets%20in%20a%20gold-benzene%20diamine-gold%20single%20molecule%20tunnel%20junction.pdf Szepieniec, Mark S. and Greer, James C. (2020) Electrode-molecule energy level offsets in a gold-benzene diamine-gold single molecule tunnel junction. The Journal of Chemical Physics, 153 (17). p. 174104. ISSN 0021-9606 Electronic transport ; Potential energy barrier; Wigner functions; Density functional theory; Configuration interaction ; Quasiparticle; Current-voltage characteristic ; Green-functions technique http://dx.doi.org/10.1063/5.0024567 doi:10.1063/5.0024567 doi:10.1063/5.0024567
spellingShingle Electronic transport ; Potential energy barrier; Wigner functions; Density functional theory; Configuration interaction ; Quasiparticle; Current-voltage characteristic ; Green-functions technique
Szepieniec, Mark S.
Greer, James C.
Electrode-molecule energy level offsets in a gold-benzene diamine-gold single molecule tunnel junction
title Electrode-molecule energy level offsets in a gold-benzene diamine-gold single molecule tunnel junction
title_full Electrode-molecule energy level offsets in a gold-benzene diamine-gold single molecule tunnel junction
title_fullStr Electrode-molecule energy level offsets in a gold-benzene diamine-gold single molecule tunnel junction
title_full_unstemmed Electrode-molecule energy level offsets in a gold-benzene diamine-gold single molecule tunnel junction
title_short Electrode-molecule energy level offsets in a gold-benzene diamine-gold single molecule tunnel junction
title_sort electrode-molecule energy level offsets in a gold-benzene diamine-gold single molecule tunnel junction
topic Electronic transport ; Potential energy barrier; Wigner functions; Density functional theory; Configuration interaction ; Quasiparticle; Current-voltage characteristic ; Green-functions technique
url https://eprints.nottingham.ac.uk/63914/
https://eprints.nottingham.ac.uk/63914/
https://eprints.nottingham.ac.uk/63914/