Do quantum interference effects manifest in acyclic aliphatic molecules with anchoring groups?

Abstract

The ability to control single molecule electronic conductance is imperative for achieving functional molecular electronics applications such as insulation, switching, and energy conversion. Quantum interference (QI) effects are generally used to control electronic transmission through single molecular junctions by tuning the molecular structure or the position of the anchoring group(s) in the molecule. While previous studies focussed on the QI between σ and/or π channels of the molecular backbone, here, we show that single molecule electronic devices can be designed based on QI effects originating from the interactions of anchoring groups. Furthermore, while previous studies have concentrated on the QI mostly in conjugated/cyclic systems, our study showcases that QI effects can be harnessed even in the simplest acyclic aliphatic systems—alkanedithiols, alkanediamines, and alkanediselenols. We identify band gap state resonances in the transmission spectrum of these molecules whose positions and intensities depend on the chain length, and anchoring group sensitive QI between the nearly degenerate molecular orbitals localized on the anchoring groups. We predict that these QI features can be harnessed through an external mechanical stimulus to tune the charge transport properties of single molecules in the break-junction experiments.