Self-assembly of calcium carbonate nanoparticles in water and hydrophobic solvents

The self-assembly of Ca2+ and CO32– ions into nanoparticles in water and hydrophobic solvents is investigated using molecular dynamics (MD) computer simulation. A new three-stage particle assembly procedure is used which relaxes the structure of the nanoparticle toward a lower energy state. In hydrophobic solvent the bare particle is essentially spherical whereas in water it is ellipsoidally shaped. With surfactant stabilizer the nanoparticles typically exhibit nonspherical cores in model hydrophobic solvents. Binary surfactant systems exhibit synergistic effects where for example a salicylate-sulfonate combination forms a cage which promotes a compact core. Synergistic effects on the shape of the particle were also observed in a hydrophobic solvent for surfactant-stabilized systems with trace water as a third component. The simulations show that rather than being a rigid structure the carbonate core shape and stabilizing shell coverage are sensitive to solvent, surfactant, and small polar molecules which...