Eigen versus Zundel complexes in HCl-water mixtures

There is an ongoing debate on the nature of hydration of the hydrogen ion, H+ in solution, and the extent to which Eigen or Zundel complexes occur. Here, our previous neutron diffraction data on a solution of 1:9 HCl in water are reanalyzed using a new starting hypothesis for the Monte Carlo simulation of the data. Either bare H+ ions, all H3O+ ions, or all H5O2+ ions are allowed in the simulation box together with the water and chlorine ions. All three simulations give a satisfactory fit to the experimental data. From the simulation with simple H+ ions, it is found that all H+ ions form one strong and very short hydrogen bond with water molecules and that on average 75% of them also engage in a second, slightly longer hydrogen bond. This result can be interpreted alternatively either in terms of the formation of a high percentage of asymmetric Zundel complexes or in terms of the formation of distorted H3O+ ions, which in turn form two or three hydrogen bonds, respectively, with neighboring molecules opposite their unbonded hydrogen sites (thus forming Eigen complexes). Therefore the new analysis is not inconsistent with our previous conclusion that the solution consists primarily of Eigen complexes, but does highlight the difficulty of making a clear distinction between Eigen and Zundel complexes due to the continuous random network of hydrogen bonds formed between water and hydrated protons. The role of hydrogen ion to chloride counterion contacts is also discussed in these solutions.