Theoretical modeling and interpretation of X-ray absorption spectra of liquid water

Abstract

We report extensive calculations to examine the capability of theory to explain the XAS spectra of liquid water. Several aspects that enter the theoretical model are addressed, such as the quantum mechanical methods, the statistics and the XAS model. As input into our quantum mechanical calculations we will use structural information on liquid water obtained from first principles and from classical molecular dynamics simulations. As XAS models, we will examine the full core hole and the half core hole approximations to transition state theory. The quantum mechanics is performed on the basis of density functional theory. We conclude from this study that recent experimental results are fully consistent with, and can be completely explained by, present day theory, in particular, the pre-edge peak is reproduced. We also find that the average bond coordination in liquid water is 3.1 and that the assertion in a recent paper that the hydrogen bond number is much less than that cannot be substantiated. Our calculations emphasize that further advances in our understanding of water can only be made by more sophisticated spectroscopy with significantly increased resolution.