Probing the hydrogen-bond network of water via time-resolved soft X-ray spectroscopy

Phys Chem Chem Phys. 2009 May 28;11(20):3951-7. doi: 10.1039/b822210j. Epub 2009 Mar 10.

Abstract

We report time-resolved studies of hydrogen bonding in liquid H(2)O, in response to direct excitation of the O-H stretch mode at 3 mum, probed via soft X-ray absorption spectroscopy at the oxygen K-edge. This approach employs a newly developed nanofluidic cell for transient soft X-ray spectroscopy in the liquid phase. Distinct changes in the near-edge spectral region (XANES) are observed, and are indicative of a transient temperature rise of 10 K following transient laser excitation and rapid thermalization of vibrational energy. The rapid heating occurs at constant volume and the associated increase in internal pressure, estimated to be 8 MPa, is manifested by distinct spectral changes that differ from those induced by temperature alone. We conclude that the near-edge spectral shape of the oxygen K-edge is a sensitive probe of internal pressure, opening new possibilities for testing the validity of water models and providing new insight into the nature of hydrogen bonding in water.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Absorption
  • Hydrogen Bonding
  • Pressure
  • Spectrum Analysis, Raman
  • Temperature
  • Time Factors
  • Vibration*
  • Water / chemistry*
  • X-Rays

Substances

  • Water