Enhanced structural disorder at a nanocrystalline ice surface

Detailed knowledge of the structure and dynamics of the surface of ice particles is of considerable importance for understanding catalytic reactions in the upper atmosphere. Here we report the enhanced structural disorder specific at a nanoscale ice island studied by using heterodyne-detected vibrational sum-frequency generation spectroscopy under ultrahigh vacuum. Ultrathin films of isotopically diluted HOD crystalline ice are grown on Rh(111), whose average height (≥1.4 nm) is controlled by varying the nominal film thickness. The Im χ(2) spectrum of the hydrogen-bonded O–H stretching band shows a bipolar line shape reflecting the orientation-dependent hydrogen bond length alternation in the subsurface of the ice island. The peak splitting and the bandwidth of the bipolar spectrum increase with a decrease in the nominal film thickness. This is ascribed to the significant enhancement of structural disorder at the surface of the ice island as the terrace size is decreased. Temperature dependence of the Im χ(2) spectra of the hydrogen bonded O–H stretching band indicates that the thermal expansivity of the top layer increases upon decreasing the island size. In addition, the stretching frequency of the dangling OD band at the island surface with the average height less than 18 nm shows a systematic blue shift with increasing temperature from 100 to 145 K: this is in stark contrast to thick ice films and bulk ice showing a negligible peak shift at a temperature lower than 180 K. These findings indicate that the anharmonicity of the intermolecular potential at the top layer of the ice island is strongly enhanced upon decreasing its terrace size, providing valuable insights for understanding the properties of ice particles in the outer atmosphere including polar mesospheric clouds.