Insights into Phases of Liquid Water from Study of Its Unusual Glass-Forming Properties

The vitrification of pure water is compared with that of molecular solutions rich in water, and gross differences are noted. Thermodynamic reasoning and direct observations on noncrystallizing nanoconfined water indicate that the glass transition in ambient-pressure water is qualitatively distinct from that found in the usual molecular liquids. It belongs instead to the order-disorder class of transition seen in molecular and ionic crystalline materials. The distinctive “folding funnel” energy landscape for this type of system explains the extreme weakness of the glass transition of water as well as the consequent confusion that has characterized its scientific history; it also explains the very small excess entropy at the glass transition temperature. The relation of confined water behavior to that of bulk is discussed, and the “fragile-to-strong ” transition for supercooled water is interpreted by adding a “critical point–free ” scenario to the two competing scenarios for understanding supercooled bulk water. Many aspects of water’s liquid-statebehavior are unusual, and this includesthe way in which it forms a glass. For most molecular liquids, particularly in small sam-ples, rapid cooling generates a glassy solid rather than a crystalline phase. Vitrification in mos