How Thick is the Air-Water Interface?─A Direct Experimental Measurement of the Decay Length of the Interfacial Structural Anisotropy

The air-water interface is a highly prevalent phase boundary impacting many natural and artificial processes. The significance of this interface arises from the unique properties of water molecules within the interfacial region, with a crucial parameter being the thickness of its structural anisotropy, or "healing depth". This quantity has been extensively assessed by various simulations which have converged to a prediction of a remarkably short length of ∼6 Å. Despite the absence of any direct experimental measurement of this quantity, this predicted value has surprisingly become widely accepted as fact. Using an advancement in nonlinear vibrational spectroscopy, we provide the first measurement of this thickness and, indeed, find it to be ∼6-8 Å, finally confirming the prior predictions. Lastly, by combining the experimental results with depth-dependent second-order spectra calculated from ab initio parametrized molecular dynamics simulations, which are also in excellent agreement with this experimental result, we shed light on this surprisingly short correlation length of molecular orientations at the interface.