Dispersion interactions between semiconducting wires

The dispersion energy between extended molecular chains (or equivalently infinite wires) with nonzero 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 nonoverlapping) separations it approaches a power-law scaling given by z(-2), i.e., the dispersion interaction expected between 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.