Ultrafast Reorientation of Dangling OH Groups at the Air-Water Interface Using Femtosecond Vibrational Spectroscopy

Cho-Shuen Hsieh, R. Kramer Campen, Ana Celia Vila Verde, Peter Bolhuis, Han-Kwang Nienhuys, and Mischa Bonn
Phys. Rev. Lett. 107, 116102 – Published 8 September 2011
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Abstract

We report the real-time measurement of the ultrafast reorientational motion of water molecules at the water-air interface, using femtosecond time- and polarization-resolved vibrational sum-frequency spectroscopy. Vibrational excitation of dangling OH bonds along a specific polarization axis induces a transient anisotropy that decays due to the reorientation of vibrationally excited OH groups. The reorientation of interfacial water is shown to occur on subpicosecond time scales, several times faster than in the bulk, which can be attributed to the lower degree of hydrogen bond coordination at the interface. Molecular dynamics simulations of interfacial water dynamics are in quantitative agreement with experimental observations and show that, unlike in bulk, the interfacial reorientation occurs in a largely diffusive manner.

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  • Received 16 June 2011

DOI:https://doi.org/10.1103/PhysRevLett.107.116102

© 2011 American Physical Society

Authors & Affiliations

Cho-Shuen Hsieh1, R. Kramer Campen1, Ana Celia Vila Verde2,*, Peter Bolhuis2, Han-Kwang Nienhuys1, and Mischa Bonn1,3,†

  • 1FOM Institute AMOLF, Science Park 104, 1098 XG Amsterdam, The Netherlands
  • 2Van ’t Hoff Institute for Molecular Science, University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands
  • 3Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany.

  • *Also at University of Minho, Physics Center, Campus de Gualtar, 4710-057 Braga, Portugal.
  • bonn@amolf.nl

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Issue

Vol. 107, Iss. 11 — 9 September 2011

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