Extended curly arrow rules to rationalise and predict structural effects on quantum interference in molecular junctions

Abstract

The ability to easily and reliably predict quantum interference (QI) behaviour would facilitate the design of functional molecular wires with potential applications in switches, transistors and thermoelectric devices. A variety of predictive methods exist, but with the exception of computationally-expensive DFT-based charge transport simulations, these often fail to account for the experimentally observed behaviour of molecules that differ significantly in structure from alternant polycyclic aromatic hydrocarbons. By considering a range of prior studies we have developed an extension to predictive “curly arrow rules”. We show that, in most cases, these extended curly arrow rules (ECARs) can rationalise the type of QI exhibited by conjugated molecular wires containing heteroatoms, cross-conjugation and/or non-alternant structures. ECARs provide a straightforward “pen-and-paper” method to predict whether a molecular wire will display constructive, destructive or “shifted destructive” QI, i.e. whether or not its transmission function would be expected to show an antiresonance, and if this antiresonance would occur close to the Fermi energy or be shifted elsewhere.