Extreme Nanoconfinement Reshapes the Self-Dissociation of Water

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Main Authors: Wang, Chenyu, Yin, Wanjian, Zhou, Ke
Format: Preprint
Published: 2025
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author Wang, Chenyu
Yin, Wanjian
Zhou, Ke
author_facet Wang, Chenyu
Yin, Wanjian
Zhou, Ke
contents Water's ability to self-dissociate into H$_3$O$^+$ and OH$^-$ ions is central to acid-base chemistry and bioenergetics. Recent experimental advances have enabled the confinement of water down to the nanometre scale, even to the single-molecule limit, yet how this process is altered at the extreme nanoconfinement remains unclear. Using \emph{ab-initio} calculations and enhanced-sampling machine-learning potential molecular dynamics, we show that monolayer-confined water exhibits a markedly lower barrier to auto-dissociation than bulk water. Confinement restructures both intramolecular bonding and the intermolecular hydrogen-bond network, while enforcing quasi-2D dipolar correlations that amplify dielectric fluctuations. Our results imply that two-dimensional confined water could act as a \emph{superdielectric} medium and may exhibit \emph{superionic} behavior, as observed in recent experiments. These findings reveal confinement as a powerful route to enhanced proton activity, shedding light on geochemical niches, biomolecular environments, and nanofluidic systems where water's chemistry is fundamentally reshaped.
format Preprint
id arxiv_https___arxiv_org_abs_2512_18716
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Extreme Nanoconfinement Reshapes the Self-Dissociation of Water
Wang, Chenyu
Yin, Wanjian
Zhou, Ke
Mesoscale and Nanoscale Physics
Materials Science
Chemical Physics
Water's ability to self-dissociate into H$_3$O$^+$ and OH$^-$ ions is central to acid-base chemistry and bioenergetics. Recent experimental advances have enabled the confinement of water down to the nanometre scale, even to the single-molecule limit, yet how this process is altered at the extreme nanoconfinement remains unclear. Using \emph{ab-initio} calculations and enhanced-sampling machine-learning potential molecular dynamics, we show that monolayer-confined water exhibits a markedly lower barrier to auto-dissociation than bulk water. Confinement restructures both intramolecular bonding and the intermolecular hydrogen-bond network, while enforcing quasi-2D dipolar correlations that amplify dielectric fluctuations. Our results imply that two-dimensional confined water could act as a \emph{superdielectric} medium and may exhibit \emph{superionic} behavior, as observed in recent experiments. These findings reveal confinement as a powerful route to enhanced proton activity, shedding light on geochemical niches, biomolecular environments, and nanofluidic systems where water's chemistry is fundamentally reshaped.
title Extreme Nanoconfinement Reshapes the Self-Dissociation of Water
topic Mesoscale and Nanoscale Physics
Materials Science
Chemical Physics
url https://arxiv.org/abs/2512.18716