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

TL;DR

This paper uses ab initio molecular dynamics to unify thermodynamic and spectroscopic data on excess protons in aqueous HF solutions, revealing a shared proton transfer mechanism with HCl.

Contribution

It introduces a complementary Eigen-Zundel interpretation that explains the similar spectra of HF and HCl solutions despite different dissociation behaviors.

Findings

Proton in HF is dynamically shared with water, not firmly bound to F^-

Similar vibrational spectra of HF and HCl explained by comparable free-energy profiles

Reconciles thermodynamic and spectroscopic observations of excess protons

Abstract

Aqueous solutions of HF and HCl behave very differently at intermediate concentrations: HCl dissociates completely, whereas HF remains only partially dissociated and forms bifluoride (HF$_2^-$). This should lead to 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-state description which also explains the formation of 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.