The hydrogen bond network structure within the hydration shell around simple osmolytes: urea, tetramethylurea, and trimethylamine-N-oxide, investigated using both a fixed charge and a polarizable water model.

Anna Kuffel, Jan Zielkiewicz

Index: J. Chem. Phys. 133(3) , 035102, (2010)

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Abstract

Despite numerous experimental and computer simulation studies, a controversy still exists regarding the effect of osmolytes on the structure of surrounding water. There is a question, to what extent some of the contradictory results may arise from differences in potential models used to simulate the system or parameters employed to describe physical properties of the mixture and interpretation of the results. Bearing this in mind, we determine two main aims of this work as follows: description of the water-water hydrogen bond network structure within the solvation layer around solute molecules (urea, trimethylamine-N-oxide, and tetramethylurea), and also comparison of rigid simple point charges (SPC) and polarizable (POL3) models of water. The following quantities have been examined: radial distribution functions of water molecules around the investigated solutes, both local and overall characteristics of the hydrogen bond network structure (using recently elaborated method), along with estimation of the mean energy of a single hydrogen bond, and also the probability distributions which describe the orientation of a single water particle plane relatively to the center of mass of the solute molecule. As an independent method for the evaluation of the degree of changes in local structural ordering, a harmonic approximation has been adopted to estimate the absolute entropy of water. It was found that within the solvation shell of the investigated solutes, the structure of hydrogen bond network changes only slightly comparing to bulk water. Therefore, we conclude that the investigated osmolyte molecules do not disturb significantly the structure of surrounding water. This conclusion was also confirmed by calculations of the absolute entropy of water using a harmonic approximation. In the immediate vicinity of the solutes, we observe that the water-water hydrogen bonds are slightly more stable; they are slightly less distorted and a little shorter than in bulk water. Nevertheless, although this local water structure is more stable and stiffer, our results do not indicate that it is more ordered compared to bulk. Finally, the comparison of both used models of water, the fixed charge and the polarizable, leads to unambiguous conclusion that rigid (SPC) water model may be successfully used in simulations instead of polarizable (POL3), as no significant differences between these two models have been observed.