Vibrational response of hydrogen-bonded interfacial water is dominated by intramolecular coupling

Phys Rev Lett. 2008 May 2;100(17):173901. doi: 10.1103/PhysRevLett.100.173901. Epub 2008 Apr 28.

Abstract

Using the surface-specific vibrational technique of vibrational sum-frequency generation, we reveal that the double-peaked structure in the vibrational spectrum of hydrogen-bonded interfacial water molecules originates from vibrational coupling between the stretch and bending overtone, rather than from structural effects. This is demonstrated by isotopic dilution experiments, which reveal a smooth transition from two peaks to one peak, as D2O is converted into HDO. Our results show that the water interface is structurally more homogeneous than previously thought.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Hydrogen Bonding
  • Spectrophotometry, Infrared / methods
  • Surface Properties
  • Water / chemistry*

Substances

  • Water