Unique structural fluctuations at ice surface promote autoionization of water molecules

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Water ice is one of the most abundant solid substances in nature and hydrated protons on the ice surfaces critically influence physical and chemical properties of ices. Hydrated protons are easily doped into the hydrogen-bond (HB) networks when acidic impurities are present. In contrast, in pure water molecular systems, they are generated solely by the thermal ionization of water molecules H2O ⇆ H+hyd+OH-hyd. Therefore, the proton activity inherent to water ice is determined by the amount and mobility of hydrated protons derived from the autoionization.

Considerable discussions have been made, yet not been settled, on whether the activity of hydrated protons is substantially enhanced at the surface of water ice. This is crucially important problem for understanding the impact of ice surface ubiquitous in nature on a wide variety of heterogeneous phenomena, such as charge generation, separation and trapping in a thunder storm, photochemical destruction of the earth's ozone layer, and even the molecular evolution in space, etc.

Very recently, researchers led by Toshiki Sugimoto, Associate Professor at the Institute for Molecular Science, succeeded in directly and quantitatively demonstrating that the proton activity is significantly enhanced at the surfaces of low-temperature ice. On the basis of simultaneous experimental observation of the H/D isotopic exchange of water molecules at the surface and in the interior of double-layer crystalline-ice films composed of H2O and D2O, they reported three major discoveries of the unique enhancement of surface proton activity: (1) proton activity proved by the H/D exchange at the topmost surface is at least three orders of magnitude higher than in the interior even below 160 K; (2) the enhanced proton activity is dominated by autoionization process of water molecules rather than proton transfer process at ice surface; (3) as a consequence of surface promoted autoionization, the concentration of surface hydrated protons is estimated to be more than six orders of magnitude higher than that in the bulk.

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With regards,
Amelia Charlotte
Managing Editor
Journal of Organic & Inorganic Chemistry
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