Molecular Structure–(Thermo)electric Property Relationships in Single-Molecule Junctions and Comparisons with Single- and Multiple-Parameter Models

Naher, Masnun and Milan, David C. and Al-Owaedi, Oday A. and Planje, Inco J. and Bock, Sören and Hurtado-Gallego, Juan and Bastante, Pablo and Abd Dawood, Zahra Murtada and Rincón-García, Laura and Rubio-Bollinger, Gabino and Higgins, Simon J. and Agraït, Nicolás and Lambert, Colin J. and Nichols, Richard J. and Low, Paul J. (2021) Molecular Structure–(Thermo)electric Property Relationships in Single-Molecule Junctions and Comparisons with Single- and Multiple-Parameter Models. Journal of the American Chemical Society, 143 (10). pp. 3817-3829. ISSN 0002-7863

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Abstract

The most probable single-molecule conductance of each member of a series of 12 conjugated molecular wires, 6 of which contain either a ruthenium or platinum center centrally placed within the backbone, has been determined. The measurement of a small, positive Seebeck coefficient has established that transmission through these molecules takes place by tunneling through the tail of the HOMO resonance near the middle of the HOMO–LUMO gap in each case. Despite the general similarities in the molecular lengths and frontier-orbital compositions, experimental and computationally determined trends in molecular conductance values across this series cannot be satisfactorily explained in terms of commonly discussed “single-parameter” models of junction conductance. Rather, the trends in molecular conductance are better rationalized from consideration of the complete molecular junction, with conductance values well described by transport calculations carried out at the DFT level of theory, on the basis of the Landauer–Büttiker model.

Item Type:
Journal Article
Journal or Publication Title:
Journal of the American Chemical Society
Uncontrolled Keywords:
/dk/atira/pure/subjectarea/asjc/1300/1303
Subjects:
?? colloid and surface chemistrybiochemistrygeneral chemistrycatalysisbiochemistrycolloid and surface chemistrygeneral chemistrycatalysischemistry(all) ??
ID Code:
178952
Deposited By:
Deposited On:
10 Nov 2022 16:00
Refereed?:
Yes
Published?:
Published
Last Modified:
13 Sep 2024 13:55