Influence of long-range interactions on quantum interference in molecular conduction. A tight-binding (Hückel) approach

Yuta Tsuji, Ernesto Estrada

Research output: Contribution to journalArticle

Abstract

When certain pairs of atoms in a π-conjugated molecule are connected with nanometer-scale source and drain electrodes, the remarkable quantum interference (QI) effect may arise. In this case, the electron transmission probability is significantly suppressed due to the QI effect. Tight-binding approaches, such as the Hückel molecular orbital (HMO) model, have revealed important features of this quantum phenomenon. However, important deviations from experiments and from more sophisticated calculations are known for a variety of cases. Here, we propose an extension of the HMO method to include non-nearest-neighbor interactions. Such long-range interactions (LRIs) are implemented in the HMO model in the form of a damping function that decays as the topological distance - the number of bonds separating two atoms - gets larger. The proposed model is further developed so that a geometric modification, i.e., the rotation around a single bond, can be taken into account. Our results show that LRI affects both the location of the antiresonance peak due to QI and the intensity of QI, even suppressing it in some cases. These results agree well with what was observed in a Density Functional based Tight-Binding (DFTB) study reported in the literature. These properties can be interpreted on the basis of a graph-theoretic path-counting model as well as the molecular orbital theory. In addition, the geometric LRI model is shown to reproduce the change of transmission as a function of rotation around the single bond separating two benzene rings in biphenyl, in agreement with what was observed in both experiment and DFTB calculation.

Original languageEnglish
Article number204123
JournalJournal of Chemical Physics
Volume150
Issue number20
DOIs
Publication statusPublished - May 28 2019

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Molecular orbitals
molecular orbitals
interference
conduction
interactions
Atoms
Benzene
atoms
counting
Damping
damping
Experiments
benzene
deviation
Electrodes
Molecules
electrodes
Electrons
rings
decay

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Influence of long-range interactions on quantum interference in molecular conduction. A tight-binding (Hückel) approach. / Tsuji, Yuta; Estrada, Ernesto.

In: Journal of Chemical Physics, Vol. 150, No. 20, 204123, 28.05.2019.

Research output: Contribution to journalArticle

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