Hydration at highly crowded interfaces

TL;DR

This study investigates the initial hydration of Cs+ ions on a Cu(111) surface, revealing unique solvation behaviors and complex ion-water interactions that challenge existing models, through combined experimental and theoretical approaches.

Contribution

It provides new insights into ion hydration at metal interfaces by combining experiment and theory to reveal complex solvation structures and behaviors.

Findings

Cs+ ions preferentially locate at water cluster perimeters

Formation of water-Cs complexes with multiple ions observed

Established models cannot fully explain the observed interactions

Abstract

Understanding the molecular and electronic structure of electrolytes at interfaces requires an analysis of the interactions between the electrode surface, the ions, and the solvent environment on equal footing. Here, we tackle this challenge by exploring the initial stages of Cs+ hydration on a Cu(111) surface by combining experiment and theory. Remarkably, we observe "inside out" solvation of Cs ions, i.e, their preferential location at the perimeter of the water clusters on the metal surface. In addition, water-Cs complexes containing multiple Cs+ ions are observed to form at these surfaces. Established models based on maximum ion-water coordination and the double layer notion cannot account for this situation and the complex interplay of microscopic interactions is the key to a fundamental understanding.