Simulations of H2O solid, liquid, and clusters, with an emphasis on ferroelectric ordering transition in hexagonal ice

Simulations are presented of H2O ice, liquid, and clusters (H2O)(n) n less than or equal to 7. The first part is devoted to orientational energetics of ice. Ordinary hexagonal ice is orientationally disordered; a transition to an ordered form lice XI) can be induced at 72 K. The recently demonstrated ferroelectric structure of ice XI (Jackson, S. M.; Wield, V. M.; Whitworth, R. W.; Oguro, M.; Wilson, C. J. Phys. Chem. B 1997, 101, 6142) seems to contradict our understanding of H2O ... H2O interactions. A polarizable water potential is proposed that accounts qualitatively for the existence of ferroelectric ice XI; its crucial ingredient is the location of the polarizability center. This potential is then tested in classical trajectory simulations of water structure, energetics, selfdiffusion, and dielectric constant. Cluster energetics and rotational constants are calculated using the rigid body diffusion Monte Carlo technique.