Ionic association and Wien effect in 2D confined electrolytes.

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Tác giả: Lydéric Bocquet, Paul Robin, Damien Toquer

Ngôn ngữ: eng

Ký hiệu phân loại: 150.1944 Philosophy and theory

Thông tin xuất bản: United States : The Journal of chemical physics , 2025

Mô tả vật lý:

Bộ sưu tập: NCBI

ID: 54779

Recent experimental advances in nanofluidics have allowed to explore ion transport across molecular-scale pores, in particular, for iontronic applications. Two-dimensional nanochannels-in which a single molecular layer of electrolyte is confined between solid walls-constitute a unique platform to investigate fluid and ion transport in extreme confinement, highlighting unconventional transport properties. In this work, we study ionic association in 2D nanochannels, and its consequences on non-linear ionic transport, using both molecular dynamics simulations and analytical theory. We show that under sufficient confinement, ions assemble into pairs or larger clusters in a process analogous to a Kosterlitz-Thouless transition, here modified by the dielectric confinement. We further show that the breaking of pairs results in an electric-field dependent conduction, a mechanism usually known as the second Wien effect. However the 2D nature of the system results in non-universal, temperature-dependent, scaling of the conductivity with electric field, leading to ionic coulomb blockade in some regimes. A 2D generalization of the Onsager theory fully accounts for the non-linear transport. These results suggest ways to exploit electrostatic interactions between ions to build new nanofluidic devices.
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