Orientational dynamics of the water layer adjacent to Au surface accelerated by polarization effect

Abstract

The orientation and rearrangement of water on a gold electrode significantly influences its physicochemical heterogeneous performance. Despite numerous experimental and theoretical studies aimed at uncovering the structural characteristics of interfacial water, the orientational behavior resulting from electrode-induced rearrangements remains a subject of ongoing debate. Here, we employed molecular dynamics simulations to investigate the adaptive structure and dynamics properties of interfacial water on Au(111) and Au(100) surfaces by considering a polarizable model for Au atoms in comparison with the non-polarizable model. Compared to the nonpolarizable systems, the polarization effect can enhance the interaction between water molecules and the gold surface. Unexpectedly, the rotational dynamics directly associated with the orientational behavior of water adjacent to the gold surface is accelerated, thereby reducing the hydrogen bond lifetime. The underlying mechanism for this anomalous phenomenon originates from the polarization effect, which induces the attraction of the positive hydrogen atoms to the surface by the negative image charge. This leads to a change in orientation that disrupts the hydrogen bonds in the first water layer and subsequently accelerates reorientation dynamics of water molecules adjacent to the gold surface. These results shed light on the intricate interplay between polarization effects and water molecule dynamics on metal surfaces, establishing the foundation for the rational regulation of the orientation of interfacial water.