Issues

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2020

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vol. 18 /

Issue 3

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E. G. Petrov
«Barrier and Superexchange Models for the Analysis of Tunnelling Current in Molecular Junctions ‘Metal–Molecular Wire–Metal’»
649–662 (2020)

PACS numbers: 05.60.Gg, 73.40.Gk, 73.63.Nm, 81.07.Nb, 85.65.+h

Based on the modified superexchange model, analytical expressions are obtained, which are convenient for analysing the tunnelling current through a molecular wire consisting of a regular chain connected to the electrodes by terminal groups. An ohmic tunnelling regime is considered, in which the terminal groups act as contact barriers, and the interaction of the chain with the electrodes is parameterized in the width factors. Analytical expressions for the current show that, for certain ratios between the key superexchange parameters, these expressions coincide in form with the expressions for the current obtained within the framework of the barrier model and the standard superexchange model, thereby showing the applicability conditions of these models. Thus, the barrier model can be used to analyse the current–voltage characteristics of the molecular wire in the presence of strongly delocalized molecular chain orbitals, whereas the standard superexchange model works with strong localization of molecular orbitals, i.e., with ‘deep’ tunnelling. The modified superexchange model also shows that a purely exponential current drop with increasing chain units appears, starting from a certain chain length, and depends significantly on the magnitude of the attenuation factor. An illustration of the results is for chains consisting of one-site and two-site repeating units. For such chains, in addition to the expressions for attenuation coefficients, formulas for preexponential factors are obtained, and it is shown that the estimation of the contact current by approximating the current–voltage characteristics of the wire to the possible value of the current at zero chain length is physically unjustified. For estimates of contact current, the minimum internal wire length must include two structural units of the chain.

Keywords: electronic transport, tunnelling, molecular wire, superexchange, non-resonant current

https://doi.org/10.15407/nnn.18.03.649

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9. F. C. Simeone, H. J. Yoon, M. M. Thuo, J. R. Barber, B. Smith, andG. M. Whitesides, J. Am. Chem. Soc., 135, No. 48: 18131 (2013); https://doi.org/10.1021/ja408652h.
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