Surface of Liquid Water: Three-Body Interactions and Vibrational Sum-Frequency Spectroscopy

Phase-sensitive vibrational sum-frequency experiments on the water surface, using isotopic mixtures of water and heavy water, have recently been performed. The experiments show a positive feature at low frequency in the imaginary part of the susceptibility, which has been difficult to interpret, and impossible to reproduce using two-body (pairwise-additive) water simulation models. We have reparameterized a new three-body simulation model for liquid water, and with this model we calculate the imaginary part of the sum-frequency susceptibility, finding good agreement with experiment for dilute HOD in D2O. Theoretical analysis provides a molecular-level structural interpretation of these new and exciting experiments. In particular, we do not find evidence of any special ice-like ordering at the surface of liquid water.