Structural Transformation of Clay Minerals by a New Molecular Dynamics Simulation Method

Abstract

A MD simulation study of 2:1 clay minerals is carried out using a new MD simulation method which is capable of simulating a system under the most general external stress conditions by considering the changes of MD cell size and shape. The tensor defining the cell size and shape is correlated with the atomic level stress tensors (both internal and external) through a Lagrangian formulation. Due to this feature, the method is able to predict the crystal transformation of molecular structures which is compatible with the imposed external stress and boundary conditions.In this paper, the new method has been applied for the first time to the simulations of dehydrated montmorillonite sheets, and has successfully revealed unforeseen structural transformations of clay minerals upon relaxation under different normal stress conditions. In order to first achieve the correct coupled simulation of atomic structural change and MD cell deformation, parametric studies were made on the effects of the time step and the “imaginary” mass M of the MD cell on the model behavior. It is found that the time step essentially controls the convergence behavior of the system, while the “imaginary” mass M has large influences on the final equilibrated structure of the system. Results of the parametric study suggest that values of 1.0×10–17 sec for the time step and 1.0×105 for the “imaginary” mass M are appropriate for the simulation of 2:1 clay minerals using the current method.Simulation results reveal the strong correlations between the degrees of constraints imposed on the simulation cell (i.e., whether the cell size or shape change is allowed) and the final equilibrated crystal structure of clay minerals. It is found during the relaxation process that large shear distortions of clay minerals will occur if full allowance is given to the cell size and shape change, while large shear stress in the sheet plane will be retained if only the cell size change is allowed. These structural changes are shown to be essentially correlated with the internal shear stresses of the clay mineral.