Corresponding Author

De-Yin Wu(dywu@xmu.edu.cn)


In this paper, the electrical properties of molecular junctions formed N,N′-bis(4-thioalkyl)-4,4′-bipyridinium (viologen) moiety between two gold (Au) electrodes have been investigated by combining density functional theory and non-equilibrium Green’s functional approach. To modulate the viologen molecule to be a cation with one and two positive charges (V+ and V2+), we introduce one and two trifluoroacetic acid ions (TFA-) around the molecule, respectively. The valence states of V+ and V2+ are confirmed by checking Mulliken and NBO charges. Then the relationship between molecular conductance and electronic structures of the neutral state V, the radical state V+ and dication V2+ are analyzed in detail. The results in analyzing transmission spectra of the three states reveal that the conductance values of V and V+ are two orders of magnitude larger than that of V2+. This suggests that the redox states of viologen molecules can be used to realize the function of molecular switches. Our calculated results also show that increasing the torsion angle between two pyridine rings of the S-4V4-S molecule will decrease the conductance. By comparing different ions of TFA、PF6 and BF4, the calculated results show that the molecular junction conductance decreases about 3 times when the torsion angle increases by about 6°. It indicates that increasing the torsion angle of the dication V2+ can improve significantly switching ratio of viologen derivatives molecules. At the same time, the calculated results show that increasing the number of methylene groups in alky chains (HS-nVn-SH, n = 2 ~ 7), the conductance values of molecular junctions decrease exponentially, and the attenuation factor of each methylene is about 1 close to alkanedithiol molecules in literatures experimentally and theoretically. This also shows that as the alkyl chain length increases, the DFT-NEGF theoretical method can better predict the zero-bias conductance of the viologen derivative molecule.

Graphical Abstract


viologen, redox active center, molecule conductance, density functional theory, non-equilibrium green’s function

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