Complementary Eigen–Zundel Interpretation Reconciles Thermodynamics and Spectroscopy of Excess Protons in Aqueous HF Solutions

Aqueous solutions of HF and HCl behave very differently at intermediate concentrations: HCl dissociates completely, whereas HFonly partially dissociates and forms bifluoride (). This should lead to markedly different excess‐proton spectra in HF and HCl solutions, in contrast to experimental reports. Using ab initio molecular dynamics, we show that in HF the proton is not firmly bound to , as suggested by textbook chemistry, but dynamically shared with a hydrating water molecule. This is rationalized by a modified Eigen‐picture description which also explains the formation of . The similar vibrational spectra of HF and HCl solutions are explained by a complementary Zundel picture in terms of almost identical excess proton transfer free‐energy profiles for HF and HCl. These results reconcile thermodynamic and spectroscopic observations and provide a unified microscopic picture of excess protons in aqueous solution.