Proton strings and rings in atypical nucleation of ferroelectricity in ice

Author:

Lasave J.ORCID,Koval S.ORCID,Laio A.,Tosatti E.ORCID

Abstract

Ordinary ice has a proton-disordered phase which is kinetically metastable, unable to reach, spontaneously, the ferroelectric (FE) ground state at low temperature where a residual Pauling entropy persists. Upon light doping with KOH at low temperature, the transition to FE ice takes place, but its microscopic mechanism still needs clarification. We introduce a lattice model based on dipolar interactions plus a competing, frustrating term that enforces the ice rule (IR). In the absence of IR-breaking defects, standard Monte Carlo (MC) simulation leaves this ice model stuck in a state of disordered proton ring configurations with the correct Pauling entropy. A replica exchange accelerated MC sampling strategy succeeds, without open path moves, interfaces, or off-lattice configurations, in equilibrating this defect-free ice, reaching its low-temperature FE order through a well-defined first-order phase transition. When proton vacancies mimicking the KOH impurities are planted into the IR-conserving lattice, they enable standard MC simulation to work, revealing the kinetics of evolution of ice from proton disorder to partial FE order below the transition temperature. Replacing ordinary nucleation, each impurity opens up a proton ring generating a linear string, an actual FE hydrogen bond wire that expands with time. Reminiscent of those described for spin ice, these impurity-induced strings are proposed to exist in doped water ice too, where IRs are even stronger. The emerging mechanism yields a dependence of the long-time FE order fraction upon dopant concentration, and upon quenching temperature, that compares favorably with that known in real-life KOH doped ice.

Publisher

Proceedings of the National Academy of Sciences

Subject

Multidisciplinary

Cited by 6 articles. 订阅此论文施引文献 订阅此论文施引文献,注册后可以免费订阅5篇论文的施引文献,订阅后可以查看论文全部施引文献

1. GenIce-core: Efficient algorithm for generation of hydrogen-disordered ice structures;The Journal of Chemical Physics;2024-03-01

2. The Hierarchical Structure and Balance Principle of Ice;Nihon Kessho Gakkaishi;2024-02-29

3. Barrier-free molecular reorientations in polyhedral water clusters;Structural Chemistry;2022-06-27

4. When kinetics plays strange tricks;Proceedings of the National Academy of Sciences;2022-01-20

5. Ring population statistics in an ice lattice model;The Journal of Chemical Physics;2021-12-14

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