Probing the hydrogen-bond network of water via time-resolved soft X-ray spectroscopy
2009 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 11, no 20, 3951-3957 p.Article in journal (Refereed) Published
We report time-resolved studies of hydrogen bonding in liquid H2O, in response to direct excitation of the O-H stretch mode at 3 mm, 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.
Place, publisher, year, edition, pages
2009. Vol. 11, no 20, 3951-3957 p.
vibrational-energy relaxation, absorption fine-structure, liquid water, temperature-dependence, pressure-dependence, optical-constants, bending mode, dynamics, h2o, ice
IdentifiersURN: urn:nbn:se:su:diva-60081DOI: 10.1039/b822210jISI: 000266065400018OAI: oai:DiVA.org:su-60081DiVA: diva2:432941
authorCount :92011-08-082011-08-082011-08-08Bibliographically approved