Proton Traffic Jam: Effect of Nanoconfinement and Acid Concentration on Proton Hopping Mechanism

The properties of the water network in concentrated HCl acid pools in nanometer‐sized reverse nonionic micelles were probed with TeraHertz absorption, dielectric relaxation spectroscopy, and reactive force field simulations capable of describing proton hopping mechanisms. We identify that only at a critical micelle size of W(0)=9 do solvated proton complexes form in the water pool, accompanied by a change in mechanism from Grotthuss forward shuttling to one that favors local oscillatory hopping. This is due to a preference for H(+) and Cl(−) ions to adsorb to the micelle interface, together with an acid concentration effect that causes a “traffic jam” in which the short‐circuiting of the hydrogen‐bonding motif of the hydronium ion decreases the forward hopping rate throughout the water interior even as the micelle size increases. These findings have implications for atmospheric chemistry, biochemical and biophysical environments, and energy materials, as transport of protons vital to these processes can be suppressed due to confinement, aggregation, and/or concentration.