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Updated: Jun 8, 2025

Probing the Structure and Dynamics of Interfacial Water with Scanning Tunneling Microscopy and Spectroscopy
Published on: May 27, 2018
Temperature-dependent vibrational energy relaxation of hydrogen-bonded and free OD groups at the air-water interface
Alessandro Greco1, Tatsuhiko Ohto2, Yuki Nagata1
1Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany.
Abstract:
Water interfaces play a crucial role in regulating interactions and energy flow. Vibrational sum-frequency generation (vSFG) spectroscopy provides structural and dynamic information on water molecules at interfaces. It has revealed, for instance, the presence of the hydrogen-bonded and free OH groups at the air-water interface. Here, using temperature-dependent, time-resolved vSFG, we focus on the vibrational energy relaxation dynamics of interfacial heavy water (D2O). We reveal that while the relaxation timescale for hydrogen-bonded OD stretch modes is temperature-independent, the lifetime of the free OD stretch mode decreases with increasing temperature. Our data, supported by simulations, suggest that both intramolecular energy transfer and rotational reorientation mechanisms jointly contribute to the energy relaxation process of the free OD, with temperature influencing these mechanisms differently.
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