The single-crystal, basal face of ice I(h) investigated with sum frequency generation

Sum frequency generation spectroscopy has been used to investigate the hydrogen-bonded region of single-crystal, hexagonal ice in the temperature range of 113-178 K. The temperature and polarization dependences of the signal are used in conjunction with a recent theoretical model to suggest an interpretation of the bluest and reddest of the hydrogen-bonded peaks. The reddest feature is associated with strong hydrogen bonding; the dynamic polarizability of this feature is primarily parallel to the surface. It is assigned to a cooperative motion among the companion to the free-OH and four-coordinate oscillators hydrogen bonded to dangling lone-pair molecules on the surface. The bluest hydrogen-bonded feature is similarly assigned to a cooperative motion of the OH stretch of dangling lone-pair molecules and of four-coordinate molecules in the lower half bilayer that are hydrogen bonded to free-OH molecules. Reconstruction induced strain is present at as low as 113 K. These results provide a richer picture of the ice surface than has heretofore been possible.