AbstractRecent theoretical advances, based on a combination of concepts from Thouless' topological theory of adiabatic charge transport and a newly introduced gauge‐invariance principle for transport coefficients, have permitted to connect (and reconcile) Faraday's picture of ionic transport—whereby each atom carries a well‐defined integer charge—with a rigorous quantum description of the electronic charge‐density distribution, which hardly suggests its partition into well defined atomic contributions. In this paper, these progresses are reviewed; in particular, it is shown how, by relaxing some general topological conditions, charge may be transported in ionic conductors without any net ionic displacements. After reporting numerical experiments which corroborate these findings, a new connection between the topological picture and the well‐known Marcus–Hush theory of electron transfer is introduced in terms of the topology of adiabatic paths drawn by atomic trajectories. As a significant byproduct, the results reviewed here permit to classify different regimes of ionic transport according to the topological properties of the electronic structure of the conducting material. Finally, a few recent applications to energy materials and planetary sciences are reported.
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