Mechanistic insights into water autoionization

Abstract

Water autoionization plays a critical role in determining pH and properties of various chemical and biological processes occurring in the water mediated environment. The strikingly unsymmetrical potential energy surface of the dissociation process poses a great challenge to the mechanistic study. Here, we demonstrate that reliable sampling of the ionization path is accessible through nanosecond timescale metadynamics simulation enhanced by machine learning of the neural network potentials with ab initio precision, which is proved by quantitatively reproduced water equilibrium constant (p$K_{\mathrm{w}}$=14.14) and ionization rate constant (1.566$\times 10^{-3}$ s${}^{-1}$). Statistical analysis unveils the asynchronous character of the concerted triple proton transfer process. Based on conditional ensemble average calculations, we propose a dual-presolvation mechanism, which suggests that a pair of hypercoordinated and undercoordinated waters bridged by one \ce{H2O} cooperatively constitutes the initiation environment for autoionization, and contributes majorly to the local electric field fluctuation to promote water dissociation.

14 pages, 5 figures, 1 table

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• Well-Tempered Metadynamics: A Smoothly Converging and Tunable Free-Energy Method
• How van der Waals interactions determine the unique properties of water
• Efficient first-principles calculation of the quantum kinetic energy and momentum distribution of nuclei
• Accurate diffusion coefficients of the excess proton and hydroxide in water via extensive ab initio simulations with different schemes

Cited by in corpus (3)

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• Aqueous Solution Chemistry In Silico and the Role of Data Driven Approaches