Characterizing the bifurcating configuration of hydrogen bonding network in interfacial liquid water and its adhesion on solid surfaces

Abstract

The interfacial structures of liquid water molecules adjacent to a solid surface contribute significantly to the interfacial properties of aqueous solutions, and are of prime importance in a wide spectrum of applications. In this work, we use molecular dynamics (MD) simulations to explore the interfacial structures, mainly in term of hydrogen bonding network, of a liquid water film interacting intimately with solid surfaces, which are composed of [100] face centered cubic (FCC) lattices. We disclose the formation of a bifurcating configuration of hydrogen bonds in interfacial liquid water and ascribe its occurrence to the collective effects of water density depletion, hydrogen bonds and local polarization. Such bifurcating configuration of interfacial water molecules consists of repetitive layer by layer water sheets with intra-layer hydrogen bonding network being formed in each layer, and inter-layer defects, i.e., hydrogen bonds formed between two neighboring layers of interfacial water. A lower bound of 2.475 for the average number of hydrogen bonds per interfacial water molecule is expected. Our MD study on the interfacial configuration of water on solid surfaces reveals a quadratic dependence of adhesion on the solid–liquid affinity, bridging the gap between the macroscopic interfacial property W_adh and the microscopic parameter ε_SL of the depth of the Lennard-Jones solid–liquid potential.