A Quantum Mechanically Derived Force Field To Predict CO2 Adsorption on Calcite {10.4} in an Aqueous Environment

Abstract

Density functional theory (DFT) with semiempirical dispersion corrections (DFT-D2) has been used to calculate the binding energy of a CO2 molecule on the calcite {10.4} surface for different positions and orientations. This generated potential energy landscape was then used to parametrize a classical force field. From this, we used metadynamics (MTD) to derive free energy profiles at 300 and 350 K for CO2 binding to calcite, CO2 binding with Ca2+, and pairing of two CO2 molecules, all for aqueous conditions. We subsequently performed classical molecular dynamics (MD) simulations of CO2 and water on the {10.4} surface at pressures and temperatures relevant for CO2 geological storage. Density profiles show characteristic structured water layering at the calcite surface and two distinct phases of water and CO2. We have also calculated the densities of the CO2-rich and water-rich phases and thereby determined the mutual solubilities. For all the pressures and temperatures in the studied range, CO2 was unable ...