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• W2110240003 abstract "This paper examines charge transport by tunneling across a series of electrically insulating molecules with the structure HS(CH2)4CONH(CH2)2R) in the form of self-assembled monolayers (SAMs), supported on silver. The molecules examined were studied experimentally by Yoon et al. (Angew. Chem. Int. Ed. 2012, 51, 4658-4661), using junctions of the structure AgS(CH2)4CONH(CH2)2R//Ga2O3/EGaIn. The tail group R had approximately the same length for all molecules, but a range of different structures. Changing the R entity over the range of different structures (aliphatic to aromatic) does not influence the conductance significantly. To rationalize this surprising result, we investigate transport through these SAMs theoretically, using both full quantum methods and a generic, independent-electron tight-binding toy model. We find that the highest occupied molecular orbital, which is largely responsible for the transport in these molecules, is always strongly localized on the thiol group. The relative insensitivity of the current density to the structure of the R group is due to a combination of the couplings between the carbon chains and the transmission inside the tail. Changing from saturated to conjugated tail groups increases the latter but decreases the former. This work indicates that significant control over SAMs largely composed of nominally insulating groups may be possible when tail groups are used that are significantly larger than those used in the experiments of Yoon et al.1." @default.
• W2110240003 created "2016-06-24" @default.
• W2110240003 creator A5005256966 @default.
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• W2110240003 date "2014-11-25" @default.
• W2110240003 modified "2023-09-26" @default.
• W2110240003 title "Charge Transport Across Insulating Self-Assembled Monolayers: Non-equilibrium Approaches and Modeling To Relate Current and Molecular Structure" @default.
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• W2110240003 doi "https://doi.org/10.1021/nn505115a" @default.
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• W2110240003 hasPublicationYear "2014" @default.
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