(181e) Equilibrium Adsorption Morphologies of Surfactants at Metal-Water Interfaces Studied Using a Novel Free Energy Sampling Methodology in Molecular Simulations

Adsorption of surfactants is a facile way of adjusting interfacial properties of metals, which has applications in electrochemistry, corrosion inhibition, heterogeneous catalysis and synthesis of anisotropic metal nanoparticles. Surfactant molecules are understood to adsorb in densely packed organized morphologies at the metal-water interfaces. Traditional molecular simulation methods as well as existing free energy sampling methodologies are inefficient in studying the formation of these morphologies due to the long timescales and large free energy barriers involved in the process. In this work, I will discuss a new umbrella sampling-based simulation methodology that our research group has developed that allows the study of these high-density morphologies. Using this methodology, we have investigated the adsorption behavior of different cationic, anionic and charge-neutral surfactants and surfactant mixtures. The role of molecular properties is governing the equilibrium adsorption morphologies will be discussed.