The curious case of the hydrated proton.

Understanding the hydrated proton is a critically important problem that continues to engage the research efforts of chemists, physicists, and biologists because of its involvement in a wide array of phenomena. Only recently have several unique properties of the hydrated proton been unraveled through computer simulations. One such process is the detailed molecular mechanism by which protons hop between neighboring water molecules, thus giving rise to the anomalously high diffusion of protons relative to other simple cations. Termed Grotthuss shuttling, this process occurs over multiple time and length scales, presenting unique challenges for computer modeling and simulation. Because the hydrated proton is in reality a dynamical electronic charge defect that spans multiple water molecules, the simulation methodology must be able to dynamically readjust the chemical bonding topology. This reactive nature of the chemical process is automatically captured with ab initio molecular dynamics (AIMD) simulation methods, where the electronic degrees of freedom are treated explicitly. Unfortunately, these calculations can be prohibitively expensive for more complex proton solvation and transport phenomena in the condensed phase. These AIMD simulations remain extremely valuable, however, in validating empirical models, verifying results, and providing insight into molecular mechanisms. In this Account, we discuss recent progress in understanding the solvation and transport properties of the hydrated excess proton. The advances are based on results obtained from reactive molecular dynamics simulations using the multistate empirical valence bond (MS-EVB) methodology. This approach relies on a dynamic linear combination of chemical bond topologies to model charge delocalization and dynamic bonding environments. When parametrized via a variational force-matching algorithm from AIMD trajectories, the MS-EVB method can be viewed as a multiscale bridging of ab initio simulation results to a simpler and more efficient representation. The process allows sampling of longer time and length scales, which would normally be too computationally expensive with AIMD alone. With the MS-EVB methodology, the statistically important components of the excess proton solvation and hopping mechanisms in liquid water have been identified. The most likely solvation structure for the hydrated proton is a distorted Eigen-type complex (H(9)O(4)(+)). In this state, the excess proton charge defect rapidly resonates between three possible distorted Eigen-type structures until a successful proton hop occurs. This process, termed the "special-pair dance", serves as a kind of preparatory phase for the proton hopping while the neighboring water hydrogen-bonding network fluctuates and ultimately rearranges to facilitate a proton hop. The modifications of the solvation structure and transport properties of the excess proton in concentrated acid solutions were further investigated. The Eigen-type solvation structure also possesses both "hydrophilic" and "hydrophobic" sides, which accounts for the affinity of the hydrated proton for the air-water interface. This unusual "amphiphilic" character of the hydrated proton further leads to the metastable formation of contact ion pairs between two hydrated protons. It also engenders a surprisingly constant degree of solubility of hydrophobic species as a function of acid concentration, which contrasts with a markedly variable solubility as a function of salt (such as NaCl or KCl) concentration.