Graphical prediction of quantum interference-induced transmission nodes in functionalized organic molecules

TL;DR

This paper extends a graphical method to predict quantum interference-induced transmission nodes in organic molecules with varied atomic species, combining theoretical models with computational methods to analyze molecular transport.

Contribution

It generalizes the graphical prediction scheme to molecules with different atomic species and validates it with computational methods.

Findings

Transmission nodes in molecular chains relate linearly to side group orbital energy.

Aromatic molecules exhibit complex nodal structures due to topology and orbital energies.

The method enables prediction of quantum interference effects in diverse molecular systems.

Abstract

Quantum interference (QI) in molecular transport junctions can lead to dramatic reductions of the electron transmission at certain energies. In a recent work [Markussen et al., Nano Lett. 2010, 10, 4260] we showed how the presence of such transmission nodes near the Fermi energy can be predicted solely from the structure of a conjugated molecule when the energies of the atomic p_z orbitals do not vary too much. Here we relax the assumption of equal on-site energies and generalize the graphical scheme to molecules containing different atomic species. We use this diagrammatic scheme together with tight-binding and density functional theory calculations to investigate QI in linear molecular chains and aromatic molecules with different side groups. For the molecular chains we find a linear relation between the position of the transmission nodes and the side group pi orbital energy. In contrast, the transmission functions of functionalized aromatic molecules generally display a rather complex nodal structure due to the interplay between molecular topology and the energy of the side group orbital.