Oxidation States, Thouless’ Pumps, and Nontrivial Ionic Transport in Nonstoichiometric Electrolytes

Pegolo, Paolo; Grasselli, Federico; Baroni, Stefano

doi:10.1103/physrevx.10.041031

Cited by 16 publications

(41 citation statements)

References 44 publications

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“…As shown in Ref. [53] this non-trivial behaviour is intertwined with the presence, in nonstoichiometric electrolytes, of dissolved yet localised 59) share the same slope, and thus the same electrical conductivity. The difference J − J is instead non-diffusive (zero slope).…”

Section: Gauge Invariance Of Electrical Conductivitymentioning

confidence: 59%

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Invariance principles in the theory and computation of transport coefficients

Grasselli

Baroni

2021

Eur. Phys. J. B

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In this work, we elaborate on two recently discovered invariance principles, according to which transport coefficients are, to a large extent, independent of the microscopic definition of the densities and currents of the conserved quantities being transported (energy, momentum, mass, charge). The first such principle, gauge invariance, allows one to define a quantum adiabatic energy current from density-functional theory, from which the heat conductivity can be uniquely defined and computed using equilibrium ab initio molecular dynamics. When combined with a novel topological definition of atomic oxidation states, gauge invariance also sheds new light onto the mechanisms of charge transport in ionic conductors. The second principle, convective invariance, allows one to extend the analysis to multi-component systems. These invariance principles can be combined with new spectral analysis methods for the current time series to be fed into the Green–Kubo formula to obtain accurate estimates of transport coefficients from relatively short molecular dynamics simulations. Graphic abstract

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Section: Gauge Invariance Of Electrical Conductivitymentioning

confidence: 59%

“…As shown in Ref. [ 53 ] this non-trivial behaviour is intertwined with the presence, in non-stoichiometric electrolytes, of dissolved yet localised electrons, whose displacement is to a large extent uncorrelated to that of the ions. By the same token discussed in Sect.…”

Section: Ab Initio Charge Transport In Ionic Conductorsmentioning

confidence: 82%

Invariance principles in the theory and computation of transport coefficients

Grasselli

Baroni

2021

Eur. Phys. J. B

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“…As shown in Ref. [50] this nontrivial behaviour is intertwined with the presence, in nonstoichiometric electrolytes, of dissolved yet localised electrons, whose displacement is to a large extent uncorrelated to that of the ions.…”

Section: Gauge Invariance Of Electrical Conductivitymentioning

confidence: 81%

Invariance principles in the theory and computation of transport coefficients

Grasselli,

Baroni

2021

Preprint

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“…The same system has been recently revisited topology-wise by Pegolo et al 34 by means of ab-initio molecular dynamics simulations, in order to detect which of the conditions warranting topological transport-and ultimately Faraday laware actually violated. After checking that the liquid is actually insulating, the authors perform a revealing computer experiment based on a Thouless pump.…”

Section: A Pitfallmentioning

confidence: 99%

Faraday law, oxidation numbers, and ionic conductivity: The role of topology

Resta

2021

Preprint

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Faraday's experiment measures-within a modern view-the charge adiabatically transported over a macroscopic distance by a given nuclear species in insulating liquids: the reason why it is integer is deeply rooted in topology. Whole numbers enter chemistry in a different form: atomic oxidation states. They are not directly measurable, and are determined instead from an agreed set of rules. Insulating liquids are a remarkable exception: Faraday's experiment indeed measures the oxidation numbers of each dissociated component in the liquid phase, whose topological values are unambiguous. Ionic conductivity in insulating liquids is expressed in terms of the autocorrelation function of the fluctuating charge current at a given temperature in zero electric field; topology plays a major role in this important observable as well. The existing literature deals with the above issues by adopting the independent-electron framework; here I provide the many-body generalization of all the above findings, which furthermore allows for compact and very transparent notations and formulas.

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Oxidation States, Thouless’ Pumps, and Nontrivial Ionic Transport in Nonstoichiometric Electrolytes

Cited by 16 publications

References 44 publications

Invariance principles in the theory and computation of transport coefficients

Invariance principles in the theory and computation of transport coefficients

Invariance principles in the theory and computation of transport coefficients

Faraday law, oxidation numbers, and ionic conductivity: The role of topology

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