Molecular Dynamics Investigation of the Various Atomic Force Contributions to the Interfacial Tension at the Supercritical CO2-Water Interface

Sequestration of carbon dioxide (CO2) in deep, geological formations involves the injection of supercritical CO2 into depleted reservoirs containing fluids such as brine or oil. The interfacial tension (IFT) between supercritical CO2 and the reservoir fluid is an important contribution to the sequestration efficiency. In turn, the IFT is a complex function of the reservoir fluid phase composition, the molecular structure of each reservoir fluid component, and environmental conditions (i.e., temperature and pressure). Molecular dynamics simulations can be used to probe the dependence of the IFT on these factors, since the IFT can be calculated directly from the simulate datomic forces and velocities at system equilibrium using the mechanical definition of the IFT. Here, we examine the contribution of each type of atomic force to the IFT, including bonded and nonbonded forces, as quantified by the anisotropy of the atomic virial tensor. In particular, we first examine a supercritical CO2-pure liquid water interface, at typical reservoir conditions (temperature of 343 K and pressure of 20 MPa), as a reference state against which CO2-brine systems can be compared. In this system, we note that the interactions between water molecules and between CO2 molecules (self interactions) contribute positively to the IFT, while the interactions between water and CO2 molecules (cross interactions) contribute negatively to the IFT. We find that the magnitude of the water self interactions is the dominant contribution. In terms of specific types of forces, we find that nonbonded electrostatic (QQ), bonded angle-bending, and bonded bond-stretching interactions contribute positively to the IFT, while nonbonded Lennard-Jones (LJ) interactions contribute negatively to the IFT. We also find that the balance between the LJ interactions and the bond-stretching interactions, in particular, plays a significant role in determining the magnitude of the IFT. Using orientational probability distribution functions to study molecular ordering about the interface, we find that the CO2 molecules prefer to lie parallel to the interface at the Gibbs dividing surface (GDS) and that both the CO2 and the water molecules are more ordered at the GDS than in the bulk. Finally, we present an initial study of a CO2-brine system with CaCl2 as the model salt at a concentration of 2.7 M. We quantify the effect of the salt on the molecular orientation of water, and show that this effect leads to an increase in the IFT, relative to the CO2-water system, which is consistent with experimental measurements.