Dissociation of Molecular Aggregates Under High Hydrostatic Pressure: The Influence of Water Structure on Benzene Cluster Solubility Arlan da Silva Gonçalves; Pedro Geraldo Pascutti
IBCCF–UFRJ–RJ
Much has been studied about the solvation effect of polar substances as well as the water importance for stabilization of biomolecular systems. It has been described that water is able to form organized structures around polar and apolar molecules. It is also possible to solvate hydrophobic molecules in water solutions by changing the physical conditions. The water at supercritical conditions is a powerful solvent for nonpolar agents. This can be explained by a relaxation of the three-dimensional structure of the hydrogen bond network, with a reduction of the dielectric constant of water. Objectives: To verify the pressure variation effect on clusters of benzene rings in water, in this work, was carried out a study of the behavior of 18 benzene molecules within a water box by Molecular Dynamics (MD) simulations. Methods: The benzene topology parameters were built with the OPLS force field, present at GROMACS package. The atomic charges were computed with GAMESS US software, HF 6-31G* base sets, using CHELPG algorithm. The system was inserted into a cubic box with 1648 SPC water molecules and submitted to energy minimization. Next, was computed an initial 500 ps of MD simulation, with heavy atoms position restraints followed by six consecutive 5 ns MD simulations at 280 K with different pressures, from 1 Bar to 5 kBar. It were monitored the volume variation, the Einstein diffusion coefficient, the radial atomic pair distribution and the root mean square fluctuation of benzene molecules. Results: Our results showed that up to 3 kBar the second solvation layer was missed and the benzene clusters started to dissolve gradually. Until 2 kBar, the solubility and diffusion of benzene molecules are inversely proportional to the pressure enhancement. Above 2-3 kBar the behavior starts to invert, in such a way that increasing the pressure causes enhancement of the benzene solubility and diffusion. The Einstein Diffusion Coefficient showed the same tendency. Conclusion: We suggest that enhancing hydrostatic pressure the benzene cluster entropy decreases up to a limit where the cluster dissolves. From this point the entropy of benzene molecules increases as an effect of its solvation by water. The multiple shell structure of water is destroyed above a critical pressure.
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