Sign preference in ion-induced nucleation: Contributions to the free energy barrier

Abstract

We have performed a series of computer simulations using the AVUS-HR approach to better understand the origin of the sign preference in ion-induced nucleation. In particular, we emphasize the importance of distinguishing between the total formation free energy of a cluster, and the nucleation free energy, which involves only those steps contributing to the free energy barrier. We have separately considered how the ion-water potential energy, the water-water potential energy, and the entropy contribute to both the cluster formation free energy, and the nucleation free energy. These simulations have shown that while the ion-water potential energies make the largest contribution to the formation free energy difference between positive and negative ions, the entropy is the contribution leading to lower nucleation free energy barriers for negative ions. The primary reason for this is the larger stable (but precritical) clusters formed around negative ions. We have further shown that the distinction between formation and nucleation free energies is of particular importance when comparing small cations with larger anions where the formation free energies can be much lower for the cationic clusters, even though the nucleation barriers are lower for the anionic clusters.