Hydration of Krypton and Consideration of Clathrate Models of   Hydrophobic Effects from the Perspective of Quasi-Chemical Theory
  AIMD results on a liquid krypton-water system are compared to recent XAFS results for the radial hydration structure for a Kr atom in liquid water solution. The comparisons with the liquid solution results are satisfactory and significantly different from the radial distributions extracted from the data on the solid clathrate hydrate phase. The calculations also produce the coordination number distribution that can be examined for metastable coordination structures suggesting possibilities for clathrate-like organization; none are seen in these results. Clathrate pictures of hydrophobic hydration are discussed, as is the quasi-chemical theory that should provide a basis for clathrate pictures. Outer shell contributions are discussed and accurately estimated; they are positive and larger than the positive experimental hydration free energy of Kr(aq), implying that inner shell contributions must be negative. Clathrate-like inner shell coordination structures extracted from the simulation of the liquid, and then subjected to quantum chemical optimization, always decomposed. Interactions with the outer shell material are decisive in stabilizing coordination structures observed in liquid solution and in clathrate phases. The ``what are we to tell students'' question about hydrophobic hydration, often answered with structural models such as clathrate pictures, is then considered; we propose an alternative answer that is consistent with successful molecular theories of hydrophobic effects and based upon distinctive observable properties of liquid water. Considerations of parsimony, for instance Ockham's razor, then suggest that additional structural hypotheses in response to ``what are we to tell students'' aren't required at this stage 
Henry S. Ashbaugh, D. Asthagiri, Lawrence R. Pratt, Susan B. Rempe