Proton Order toward the Surface of Ice Ih Revealed by Heterodyne-Detected Sum Frequency Generation Spectroscopy

Using heterodyne-detected sum frequency generation (HD-SFG) spectroscopy, we investigated surface proton order at the basal, primary prism, and secondary prism faces of single-crystalline ice I-h at ca. 130 K. The complex phase of the obtained spectra clearly indicates that second-order nonlinear polarization from which the HD-SFG signal arises is generated exclusively at the surfaces. This suggests surface proton ordering along the normal, whereas the bulk remains proton-disordered, as is well known for ice I-h. A strong positive peak observed in the HD-SFG spectra enables us to determine the "direction" of the surface proton order as "H-up", that is, the hydrogen atom of the OH group pointing away from the bulk, irrespective of the ice faces. Reliable HD-SFG measurements carried out in the present study have greatly advanced our understanding of surface structure of ice I-h.