Polarization Effects in Simulations of Kaolinite-Water Interfaces.

Abstract

Computational models of clay minerals and their interactions with the surrounding medium are highly valuable to study adsorption processes at an atomistic resolution, which may be relevant in different areas such as chromatography, environmental chemistry, and so forth. In this work, we analyzed the effect of the treatment of long-range interactions on the polarization of kaolinite-water interfacial systems in terms of structural, electric and dynamic properties, and hydrogen bonds. When using conventional three-dimensional (3D) Ewald summation, water molecules were more structured on the alumina interface of the kaolinite compared to simulations, in which the periodicity perpendicular to the plane was effectively removed. By applying an external electric field to the latter simulations, we were able to reproduce results obtained with the 3D Ewald summation. We proved that the induced polarization promotes adsorption processes of polar and charged species from aqueous solutions using a glyphosate molecule (widely used herbicide) as a particular example. The polarization phenomena raised from the simulation setup should be accounted for carefully in simulations of adsorption processes, which involve periodic images of polar interfaces. An inappropriate treatment of long-range electrostatic interactions can easily lead to artifacts and/or erroneous results.