Anomalous Transport of Small Polarons Arises from Transient Lattice Relaxation or Immovable Boundaries

Abstract

Elucidating transport mechanisms is crucial for advancing material design, yet state-of-the-art theory is restricted to exact simulations of small lattices with severe finite-size effects or approximate ones that assume the nature of transport. We leverage algorithmic advances to tame finite-size effects and exactly simulate small polaron formation and transport in the Holstein model. We further analyze the applicability of the ubiquitously used equilibriumbased Green−Kubo relations and nonequilibrium methods to predict charge mobility. We find that these methods can converge to different values and track this disparity to finite-size dependence and the sensitivity of Green−Kubo relations to the system's topology. Contrary to standard perturbative calculations, our results demonstrate that small polarons exhibit anomalous transport that manifests transiently due to nonequilibrium lattice relaxation or permanently as a signature of immovable boundaries. These findings can offer new interpretations of transport experiments on polymers and transition metal oxides.