Complementary Eigen-Zundel Interpretation Reconciles Thermodynamics and Spectroscopy of Excess Protons in Aqueous HF...

Aqueous solutions of HF and HCl behave very differently at intermediate concentrations: HCl dissociates completely, whereas HFonly partially dissociates and forms bifluoride ( ${\mathrm{HF}}_2^{-}$ ). 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 $F^{-}$ , 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 ${\mathrm{HF}}_2^{-}$ . 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.