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Updated: Nov 1, 2025

Probing the Structure and Dynamics of Interfacial Water with Scanning Tunneling Microscopy and Spectroscopy
Published on: May 27, 2018
Lifetime-Associated Two-Dimensional Infrared Spectroscopy Reveals the Hydrogen-Bond Structure of Supercooled Water in
Federico Caporaletti1,2, Daniel Bonn1, Sander Woutersen2
1Van der Waals-Zeeman Institute, Institute of Physics, University of Amsterdam, 1098XH Amsterdam, The Netherlands.
Abstract:
We demonstrate a method to address the problem of spectral overlap in multidimensional vibrational spectroscopy and use it to investigate supercooled aqueous sorbitol solutions. The absence of crystallization in these solutions has been attributed to "soft" confinement of water in subnanometer voids in the sorbitol matrix, but the details of the hydrogen-bond structure are still largely unknown. 2D-IR spectroscopy of the OH-stretch mode is an excellent tool to investigate hydrogen bonding, but in this case it seems difficult because of the overlapping water and sorbitol contributions to the 2D-IR spectrum. Using the difference in OH-stretch lifetimes of water and sorbitol we can cleanly separate these contributions. Surprisingly, the separated 2D-IR spectra show that the hydrogen-bond disorder of soft-confined water is independent of temperature and decoupled from its orientational order. We believe the approach we use to separate overlapping 2D-IR spectra will enhance the applicability of 2D-IR spectroscopy to study multicomponent systems.
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