Understanding the Essential Nature of the Hydrated Excess Proton Through Simulation and Interpretation of Recent Spectroscopic Experiments

TL;DR

This study combines advanced simulations and recent spectroscopic data to reveal that the hydrated excess proton in water exhibits dynamic structural reorientations and spectral signatures, challenging static models and supporting a distorted Eigen cation picture.

Contribution

It demonstrates that the hydrated proton's dynamics involve structural reorientations and spectral features consistent with a distorted Eigen cation, using both reactive and ab initio molecular dynamics.

Findings

Proton transport timescales align with structural reorientations.

Spectral signatures distinguish hydrated excess proton from other protons.

Results challenge static potential well models, favoring a dynamic Eigen cation view.

Abstract

Two-dimensional infrared spectroscopy experiments have presented new results regarding the dynamics of the hydrated excess proton (aka <q>hydronium</q> cation solvated in water). It has been suggested by these experiments that the hydrated excess proton has an anisotropy reorientation timescale of 2.5 ps, which can be viewed as being somewhat long lived. Through the use of both the reactive molecular dynamics Multistate-Empirical Valence Bond method and Experiment Directed Simulation Ab Initio Molecular Dynamics we show that timescales of the same magnitude are obtained that correspond to proton transport, while also involving structural reorientations of the hydrated proton structure that correspond to the so-called <q>special pair dance</q>. The latter is a process predicted by prior computational studies in which the central hydrated hydronium in a distorted Eigen cation (H₉O₄⁺) structure continually switches special pair partners with its strongly hydrogen-bonded neighboring water molecules. These dynamics are further characterized through the time-evolution of instantaneous normal modes. It is concluded that the hydrated excess proton has a spectral signature unique from the other protons in the hydrated proton complex. However, the results call into question the use of a static picture based on a simple effective one dimensional potential well to describe the hydrated excess proton in water. Instead, they more conclusively point to a distorted and dynamic Eigen cation as the most prevalent hydrated proton species in acid solutions of dilute to moderate concentrations.