title: Free-energy landscape and nucleation pathway of polymorphic minerals from solution in a Potts lattice-gas model.
abstract: Metastable minerals commonly form during reactions between water and rock. The nucleation mechanism of polymorphic phases from solution are explored here using a two-dimensional Potts model. The model system is composed of a solvent and three polymorphic solid phases. The local state and position of the solid phase are updated by Metropolis dynamics. Below the critical temperature, a large cluster of the least stable solid phase initially forms in the solution before transitioning into more-stable phases following the Ostwald step rule. The free-energy landscape as a function of the modal abundance of each solid phase clearly reveals that before cluster formation, the least stable phase has an energetic advantage because of its low interfacial energy with the solution, and after cluster formation, phase transformation occurs along the valley of the free-energy landscape, which contains several minima for the regions of three phases. Our results indicate that the solid-solid and solid-liquid interfacial energy contribute to the formation of the complex free-energy landscape and nucleation pathways following the Ostwald step rule.
authors.affiliation: Graduate School of Environmental Studies, Tohoku University, 6-6-20 Aramaki, Aoba-ku, Sendai 980-8579, Japan.
authors.forename: Atsushi
authors.initials: A
authors.lastname: Okamoto
authors.affiliation: Department of Solid Earth Geochemistry, Japan Agency for Marine-Earth Science and Technology, 2-15 Natsushima-cho, Yokosuka 237-0061, Japan.
authors.forename: Tatsu
authors.initials: T
authors.lastname: Kuwatani
authors.affiliation: Department of Electrical and Electronic Engineering, Graduate School of Engineering, Kobe University, 1-1 Rokkodai-cho, Nada-ku, Kobe, Hyogo 657-8501, Japan.
authors.forename: Toshiaki
authors.initials: T
authors.lastname: Omori
authors.affiliation: Graduate School of Arts and Sciences, University of Tokyo, 3-8-1 Komaba, Meguro-ku, Tokyo 153-8902, Japan.
authors.forename: Koji
authors.initials: K
authors.lastname: Hukushima