Unlimiting ionic conduction: manipulating hydration dynamics through vibrational strong coupling of water.

The energy states of molecules and the vacuum electromagnetic field can be hybridized to form a strong coupling state. In particular, it has been demonstrated that vibrational strong coupling can be used to modify the chemical dynamics of molecules. Here, we propose that ion dynamics can be altered through modifications of the dynamic hydration structure in a cavity vacuum field. We investigated the effect of different electrolyte species on ionic conductivity. Infrared spectroscopy of aqueous electrolyte solutions within the cavity confirmed the formation of vibrational ultrastrong coupling of water molecules, even in the presence of electrolytes. Interestingly, we observed significant enhancements in ionic conductivity, for specific alkali cations, particularly those classified as structure-breaking cations. These enhancements cannot be explained within the current theoretical framework for liquid electrolytes. Our analysis suggests that the vibrational strong coupling modifies the local dielectric friction experienced by hydrated ions. In addition, we propose the enthalpic and entropic modification of ionic conductivity through the systematic investigation of the hydration properties of different electrolytes. This study unveils the potential role of polaritons for exploring uncharted spaces in the design of materials with enhanced ionic conduction. Harnessing the unique properties of strong coupling and its influence on hydration dynamics could lead to the development of novel electrolytes and advancements in the field of ionic conduction.

Inherent Promotion of Ionic Conductivity via Collective Vibrational Strong Coupling of Water with the Vacuum Electromagnetic Field.

Hydrogen bonding interactions among water molecules play a critical role in chemical reactivity, dynamic proton mobility, static dielectric behavior, and the thermodynamic properties of water. In this study, we demonstrate the modification of ionic conductivity of water through hybridization with a vacuum electromagnetic field by strongly coupling the O─H stretching mode of H2O to a Fabry-Perot cavity mode. The hybridization generates collective vibro-polaritonic states, thereby enhancing the proton conductivity by an order of magnitude at resonance. In addition, the dielectric constants increase at resonance in the coupled state. The findings presented herein reveal how a vacuum electromagnetic environment can be engineered to control the ground-state properties of water.