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Updated: Jun 1, 2026

Multimodal Nonlinear Hyperspectral Chemical Imaging Using Line-Scanning Vibrational Sum-Frequency Generation Microscopy
Published on: December 1, 2023
Surface of liquid water: three-body interactions and vibrational sum-frequency spectroscopy
Piotr A Pieniazek1, Craig J Tainter, James L Skinner
1Theoretical Chemistry Institute and Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706, USA.
Abstract:
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 D(2)O. 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.
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