Subpicosecond Molecular Rearrangements Affect Local Electric Fields and Auto-Dissociation in Water (vol 127, pg 3392, 2023)

Molecular simulations of auto-dissociation of water molecules in an 81,000 atom bulk water system show that the electric field variations caused by local bond length and angle variations enhance proton transfer within ∼600 fs prior to auto-dissociation. In this paper, auto-dissociation relates to the initial separation of a proton from a water molecule to another, forming the HO and OH ions. Only transfers for which a proton's initial nearest covalently bonded oxygen remained the same for at least 1 ps prior to the transfer and for which that proton's new nearest acceptor oxygen remained the same for at least 1 ps after the transfer were evaluated. Electric fields from solvent atoms within 6 Å of a transferring proton (H*) are dominant, with little contribution from farther molecules. However, exclusion of the accepting oxygen in such electric field calculations shows that the field on H* from the other solvent atoms weakens as the time to transfer becomes less than 600 fs, indicating the primary importance of the accepting oxygen on enabling auto-dissociation. All resultant OH and HO ion pairs recombined at times greater than 1 ps after auto-dissociation. A concentration of 8.01 × 10 cm for these ion pairs was observed. The simulations indicate that transient auto-dissociation in water is more common than that inferred from dc-conductivity experiments (10 vs 10) and is consistent with the results of calculations that include nuclear quantum effects. The conductivity experiments require the rearrangement of farther water molecules to form hydrogen-bonded "water wires" that afford long-range and measurable proton transport away from the reaction site. Nonetheless, the relatively large number of picosecond-lived auto-dissociation products might be engineered within 2D layers and oriented external fields to offer new energy-related systems.