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Nanoconfinement in Slit Pores Enhances Water Self-Dissociation.
Physical Review Letters 2017 August 5
We investigate the self-dissociation of water that is nanoconfined between the sheets of a realistic layered mineral, FeS mackinawite, as well as between Lennard-Jones walls via ab initio simulations. By comparing it with the same reaction in bulk water under various thermodynamic conditions, we show that such strong two-dimensional confinement between hard surfaces greatly enhances the self-dissociation process of water-thus increasing its ionic product K_{w} due to nanoconfinement. In addition to providing free energies, we analyze in detail the underlying dielectric properties in terms of dipole moment distributions, and thus the polarity of the liquid, as well as local polarization fluctuations as quantified by dielectric tensor profiles perpendicular to the lamella.
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