It has long been proposed that the hydrated excess proton in water (aka the solvated “hydronium” cation) likely has two limiting forms, that of the Eigen cation (H9O4 +) and that of the Zundel cation (H5O2 +). There has been debate over which of these two is the more dominant species and/or whether intermediate (or “distorted”) structures between these two limits are the more realistic representation. Spectroscopy experiments have recently provided further results regarding the excess proton. These experiments show that the hydrated proton has an anisotropy reorientation time scale on the order of 1–2 ps. This time scale has been suggested to possibly contradict the picture of the more rapid “special pair dance” phenomenon for the hydrated excess proton, which is a signature of a distorted Eigen cation. The special pair dance was predicted from prior computational studies in which the hydrated central core hydronium structure continually switches (O–H···O)* special pair hydrogen-bond partners with the closest three water molecules, yielding on average a distorted Eigen cation with three equivalent and dynamically exchanging distortions. Through state-of-art simulations it is shown here that anisotropy reorientation time scales of the same magnitude are obtained that also include structural reorientations associated with the special pair dance, leading to a reinterpretation of the experimental results. These results and additional analyses point to a distorted and dynamic Eigen cation as the most prevalent hydrated proton species in aqueous acid solutions of dilute to moderate concentration, as opposed to a stabilized or a distorted (but not “dancing”) Zundel cation.

The developments of the open-source chemistry software environment since spring 2020 are described, with a focus on novel functionalities accessible in the stable branch of the package or via interfaces with other packages. These developments span a wide range of topics in computational chemistry and are presented in thematic sections: electronic structure theory, electronic spectroscopy simulations, analytic gradients and molecular structure optimizations, ab initio molecular dynamics, and other new features. This report offers an overview of the chemical phenomena and processes can address, while showing that is an attractive platform for state-of-the-art atomistic computer simulations.

Experiment Directed Simulations (EDS) is a method within a class of techniques seeking to improve molecular simulations by minimally biasing the system Hamiltonian to reproduce certain experimental observables. In a previous application of EDS to ab initio molecular dynamics (AIMD) simulation based on electronic density functional theory (DFT), the AIMD simulations of water were biased to reproduce its experimentally derived solvation structure. In particular, by solely biasing the O-O pair correlation functions, other structural and dynamical properties that were not biased were improved. In this work, the hypothesis is tested that directly biasing the O-H pair correlation (and hence the O-H…H hydrogen bonding), will provide an even better improvement of DFT-based water properties in AIMD simulations. The logic behind this hypothesis is that for most electronic DFT descriptions of water the hydrogen bonding is known to be deficient due to anomalous charge transfer and over polarization in the DFT. Using recent advances to the EDS learning algorithm, we thus train a minimal bias on AIMD water that reproduces the O-H radial distribution function derived from the highly accurate MB-pol model of water. It is then confirmed that biasing the O-H pair correlation alone can lead to improved AIMD water properties, with structural and dynamical properties in even closer to experiment than the previous EDS-AIMD model.