Structural Origins of Conductance Fluctuations in Gold-Thiolate Molecular Transport Junctions.

We report detailed atomistic simulations combined with high-fidelity conductance calculations to probe the structural origins of conductance fluctuations in thermally evolving Au-benzene-1,4-dithiolate-Au junctions. We compare the behavior of structurally ideal junctions (where the electrodes are modeled as flat surfaces) to structurally realistic, experimentally representative junctions resulting from break-junction simulations. The enhanced mobility of metal atoms in structurally realistic junctions results in significant changes to the magnitude and origin of the conductance fluctuations. Fluctuations are larger by a factor of 2-3 in realistic junctions compared to ideal junctions. Moreover, in junctions with highly deformed electrodes, the conductance fluctuations arise primarily from changes in the Au geometry, in contrast to results for junctions with nondeformed electrodes, where the conductance fluctuations are dominated by changes in the molecule geometry. These results provide important guidance to experimentalists developing strategies to control molecular conductance, and also to theoreticians invoking simplified structural models of junctions to predict their behavior.

• Publication year

  2013

• Venue

  Journal of Physical Chemistry Letters

• Publication date

  2013-03-01

• Fields of study

  Materials Science, Physics, Chemistry, Medicine

• Identifiers
  DOI 10.1021/jz4001104arXiv 1303.0315PMID 26291351
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

• Linker dependent bond rupture force measurements in single-molecule junctions.

  2012cited by this paper
• Signatures of cooperative effects and transport mechanisms in conductance histograms.

  2012cited by this paper
• The gold-sulfur interface at the nanoscale.

  2012cited by this paper
• Large-scale atomistic simulations of environmental effects on the formation and properties of molecular junctions.

  2012cited by this paper
• Single-molecule conductance of π-conjugated rotaxane: new method for measuring stipulated electric conductance of π-conjugated molecular wire using STM break junction.

  2012cited by this paper
• Mechanically controlled molecular orbital alignment in single molecule junctions.

  2011cited by this paper
• Influence of binding groups on molecular junction formation.

  2011cited by this paper
• Ab initio calculations of structural evolution and conductance of benzene-1,4-dithiol on gold leads.

  2011cited by this paper
• Benzenedithiol: a broad-range single-channel molecular conductor.

  2011cited by this paper
• Oligomeric Gold−Thiolate Units Define the Properties of the Molecular Junction between Gold and Benzene Dithiols

  2010cited by this paper
• The experimental determination of the conductance of single molecules.

  2010cited by this paper
• Configuration and conductance evolution of benzene-dithiol molecular junctions under elongation

  2010cited by this paper
• Molecular Simulation Studies on the Elongation of Gold Nanowires in Benzenedithiol

  2010cited by this paper
• Structural changes during the formation of gold single atom chains: stability criteria and electronic structure

  2010cited by this paper
• Molecule-electrode bonding design for high single-molecule conductance.

  2010cited by this paper
• Conformational and conductance fluctuations in a single-molecule junction: Multiscale computational study

  2010cited by this paper
• Atomistic mechanics and formation mechanism of metal-molecule-metal junctions.

  2009cited by this paper
• The nature of transport variations in molecular heterojunction electronics.

  2009cited by this paper
• Progress with Molecular Electronic Junctions: Meeting Experimental Challenges in Design and Fabrication

  2009cited by this paper
• Algorithm for the construction of self-energies for electronic transport calculations based on singularity elimination and singular value decomposition

  2008cited by this paper
• Stochastic modulation in molecular electronic transport junctions: molecular dynamics coupled with charge transport calculations.

  2008cited by this paper
• Variable contact gap single-molecule conductance determination for a series of conjugated molecular bridges

  2008cited by this paper
• X-ray Diffraction and Computation Yield the Structure of Alkanethiols on Gold(111)

  2008cited by this paper
• Role of the nanoscale in catalytic CO oxidation by supported Au and Pt nanostructures

  2007cited by this paper
• Calibration of chemical bonding between benzenedithiolate and gold: the effects of geometry and size of gold clusters

  2007cited by this paper
• From tunneling to contact : Inelastic signals in an atomic gold junction from first principles

  2007cited by this paper
• Size dependence of the structures and energetic and electronic properties of gold clusters.

  2007cited by this paper
• Single molecule junctions formed via Au-thiol contact: stability and breakdown mechanism.

  2007cited by this paper
• Effects of self-interaction corrections on the transport properties of phenyl-based molecular junctions

  2007cited by this paper
• Spin and molecular electronics in atomically generated orbital landscapes

  2006cited by this paper
• High-conductance states of single benzenedithiol molecules

  2006cited by this paper
• Effect of the atomic configuration of gold electrodes on the electrical conduction of alkanedithiol molecules

  2006cited by this paper
• Variability of conductance in molecular junctions.

  2006cited by this paper
• Dependence of single-molecule junction conductance on molecular conformation

  2006cited by this paper
• Vibronic effects on resonant electron conduction through single molecule junctions

  2006cited by this paper
• Interaction between benzenedithiolate and gold: classical force field for chemical bonding.

  2005cited by this paper
• Measurement of Single Molecule Conductance: Benzenedithiol and Benzenedimethanethiol

  2004cited by this paper
• First-principles calculation of transport properties of a molecular device

  2000cited by this paper
• Density‐functional method for very large systems with LCAO basis sets

  1997cited by this paper
• Self-consistent order-N density-functional calculations for very large systems.

  1996cited by this paper
• Tight-binding potentials for transition metals and alloys.

  1993cited by this paper
• Fast parallel algorithms for short-range molecular dynamics

  1993cited by this paper
• UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations

  1992cited by this paper

• Data-Driven Insights in Single-Molecule Break Junction Studies: A Comprehensive Review of the Data Analysis Methods.

  2025cites this paper
• Calculation of Single Molecule Conductance from Molecular Dynamics Simulations: Implementation in the SIESTA Code

  2025cites this paper
• Mechanoelectric sensitivity reveals destructive quantum interference in single-molecule junctions

  2024cites this paper
• Deep learning accelerated quantum transport simulations in nanoelectronics: from break junctions to field-effect transistors

  2024cites this paper
• Learning Conductance: Gaussian Process Regression for Molecular Electronics.

  2023cites this paper
• Dependence of Molecular Diode Behaviors on Aromaticity.

  2022cites this paper
• Development of Classical Force Fields for Interfaces between Single Molecules and Au.

  2022cites this paper
• Toward Density-Functional Theory-Based Structure-Conductance Relationships in Single Molecule Junctions.

  2022cites this paper
• Mechanism Study of Molecular Deformation of 2,2',5',2"-tetramethylated p-terphenyl-4,4"-dithiol Trapped in Gold Junctions.

  2020cites this paper
• Understanding the Conductance Dispersion of Single-Molecule Junctions

  2020cites this paper
• Theoretical insights on the importance of anchoring vs molecular geometry in magnetic molecules acting as junctions

  2019cites this paper
• Selective Nanomechanics of Aromatic versus Aliphatic Thiolates on Gold Surfaces.

  2019cites this paper
• Molecular Electronics: Toward the Atomistic Modeling of Conductance Histograms

  2019cites this paper
• Synthesis and Photochemical Characterisation of Photoactive Compounds for Molecular Electronics

  2018cites this paper
• Predicting the conductance of strongly correlated molecules: the Kondo effect in perchlorotriphenylmethyl/Au junctions.

  2018cites this paper
• DFT-based study of electron transport through ferrocene compounds with different anchor groups in different adsorption configurations of an STM setup

  2018cites this paper
• THESIS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY Synthesis and Photochemical Characterization of Photoactive Compounds for Molecular Electronics

  2018cites this paper
• Proposal for a dual spin filter based on [VO(C$_3$S$_4$O)$_2$]$^{2-}$

  2017cites this paper
• Unconventional Current Scaling and Edge Effects for Charge Transport through Molecular Clusters

  2017cites this paper
• Fingerprinting Electronic Molecular Complexes in Liquid

  2016cites this paper
• Modeling single molecule junction mechanics as a probe of interface bonding

  2016cites this paper
• Revealing the Conformational Dynamics in a Single-Molecule Junction by Site- and Angle-Resolved Dynamic Probe Method.

  2016cites this paper
• Electronic Transport as a Driver for Self-Interaction-Corrected Methods

  2015cites this paper
• Can molecular projected density of states (PDOS) be systematically used in electronic conductance analysis?

  2015cites this paper
• Interplay between quantum interference and conformational fluctuations in single-molecule break junctions.

  2015cites this paper
• Quantitative Interpretations of Break Junction Conductance Histograms in Molecular Electron Transport.

  2015cites this paper
• Designing field-controllable graphene-dot-graphene single molecule switches: A quantum-theoretical proof-of-concept under realistic operating conditions.

  2015cites this paper
• Is molecular rectification caused by asymmetric electrode couplings or by a molecular bias drop

  2015cites this paper
• Probing flexible conformations in molecular junctions by inelastic electron tunneling spectroscopy

  2015cites this paper
• Engineering Magnetic Hybridization at Organic–Ferromagnetic Interfaces by C60-Adsorption-Induced Fe(001) Surface Reconstruction

  2015cites this paper
• The image charge effect and vibron-assisted processes in Coulomb blockade transport: a first principles approach.

  2015cites this paper
• Theoretical study on mechanical and electron-transport properties of conjugated molecular junctions with carboxylic or methyl sulfide links

  2014cites this paper
• Stretching of BDT-gold molecular junctions: thiol or thiolate termination?

  2014cites this paper
• Mapping the details of contact effect of modulated Au-octanedithiol-Au break junction by force-conductance cross-correlation.

  2014cites this paper
• Controlling the Thermoelectric Properties of Thiophene-Derived Single-Molecule Junctions

  2014cites this paper
• Adsorbates on Noble- and Ferromagnetic Metals: From Structural and Electronic Properties to Ultrafast Spin-Dependent Electron Transport

  2013cites this paper
• Atomistic simulations of highly conductive molecular transport junctions under realistic conditions.

  2013cites this paper
• Probing the Statistical Validity of the Ductile-to-Brittle Transition in Metallic Nanowires Using GPU Computing.

  2013cites this paper