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Updated: Aug 13, 2026
10:28
Probing the Structure and Dynamics of Interfacial Water with Scanning Tunneling Microscopy and Spectroscopy
Published on: May 27, 2018
Spectrally- and time-resolved vibrational surface spectroscopy: ultrafast hydrogen-bonding dynamics at D2O/CaF2
Andrey N Bordenyuk1, Alexander V Benderskii
1Department of Chemistry, Wayne State University, Detroit, MI 48202, USA.
The Journal of Chemical Physics
|April 26, 2005
Summary
This study introduces a novel spectroscopy technique to observe ultrafast changes in water's hydrogen bonds at surfaces. It reveals distinct dynamics for different hydrogen-bonding structures on a 100 fs timescale.
Area of Science:
- Physical Chemistry
- Surface Science
- Spectroscopy
Background:
- Vibrational coherences provide insights into molecular dynamics.
- Surface-selective techniques are crucial for studying interfacial phenomena.
- Ultrafast spectroscopy enables the observation of rapid molecular rearrangements.
Purpose of the Study:
- To develop and apply a time- and frequency-domain three-wave mixing spectroscopy technique.
- To investigate the ultrafast spectral dynamics of the OD stretch of D2O at a CaF2 surface.
- To probe hydrogen-bond network rearrangements and interfacial water dynamics.
Main Methods:
- Utilized infrared (IR) and visible pulses (70 fs and 40 fs, respectively).
- Employed IR+visible sum frequency generation (three-wave mixing spectroscopy).
- Tuned IR pulse wavelength to selectively excite different hydrogen-bonding subensembles.
Main Results:
- Observed spectral shifts indicating hydrogen-bond network rearrangement on a 100 fs timescale.
- Blue-side excitation (weaker H-bonds) showed monotonic decay and red-shifted frequency.
- Red-side excitation (stronger H-bonds) revealed a blue spectral shift and a 125 fs recursion, suggesting an underdamped intermolecular mode.
Conclusions:
- The developed spectroscopy is surface-selective and measures vibrational coherence spectral evolution.
- Interfacial water exhibits distinct ultrafast dynamics dependent on hydrogen-bond strength.
- Evidence for an underdamped intermolecular mode in interfacial water was found.
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