Revisiting the total ion yield x-ray absorption spectra of liquid water microjets

J Phys Condens Matter. 2008 May 21;20(20):205105. doi: 10.1088/0953-8984/20/20/205105. Epub 2008 Apr 17.

Abstract

Measurements of the total ion yield (TIY) x-ray absorption spectrum (XAS) of liquid water by Wilson et al (2002 J. Phys.: Condens. Matter 14 L221 and 2001 J. Phys. Chem. B 105 3346) have been revisited in light of new experimental and theoretical efforts by our group. Previously, the TIY spectrum was interpreted as a distinct measure of the electronic structure of the liquid water surface. However, our new results indicate that the previously obtained spectrum may have suffered from as yet unidentified experimental artifacts. Although computational results indicate that the liquid water surface should exhibit a TIY-XAS that is fundamentally distinguishable from the bulk liquid XAS, the new experimental results suggest that the observable TIY-XAS is actually nearly identical in appearance to the total electron yield (TEY-)XAS, which is a bulk probe. This surprising similarity between the observed TIY-XAS and TEY-XAS likely results from large contributions from x-ray induced electron stimulated desorption of ions, and does not necessarily indicate that the electronic structure of the bulk liquid and liquid surface are identical.