Dispersion interactions between semiconducting wires

TL;DR

This paper reveals that dispersion interactions between semiconducting wires do not follow traditional atom-atom pairwise decay laws and instead depend on the band gap, with interactions becoming more metallic-like as the gap decreases.

Contribution

It demonstrates that dispersion interactions in extended wires with small band gaps deviate from pairwise models and are influenced by plasmon modes and charge fluctuations.

Findings

Dispersion scales as z^{-5} for insulators at large separations.

Interaction approaches z^{-2} as the system becomes more metallic.

Locality-based methods may not accurately capture dispersion in small-gap systems.

Abstract

The dispersion energy between extended molecular chains (or equivalently infinite wires) with non-zero band gaps is generally assumed to be expressible as a pair-wise sum of atom-atom terms which decay as $R^{-6}$. Using a model system of two parallel wires with a variable band gap, we show that this is not the case. The dispersion interaction scales as $z^{-5}$ for large interwire separations $z$, as expected for an insulator, but as the band gap decreases the interaction is greatly enhanced; while at shorter (but non-overlapping) separations it approaches a power-law scaling given by $z^{-2}$, \emph{i.e.} the dispersion interaction expected between \emph{metallic} wires. We demonstrate that these effects can be understood from the increasing length scale of the plasmon modes (charge fluctuations), and their increasing contribution to the molecular dipole polarizability and the dispersion interaction, as the band gaps are reduced. This result calls into question methods which invoke locality assumptions in deriving dispersion interactions between extended small-gap systems.