Structure of water in Zn2+ aqueous solutions from ambient conditions up to the gigapascal pressure range: A XANES and molecular dynamics study

The structural modifications induced on a 0.5 M Zn2+ aqueous solution by increasing the pressure to 6.4 GPa were investigated using a combination of X-ray absorption near edge structure (XANES) spectroscopy and molecular dynamics (MD) simulations. The Zn K-edge XANES experimental spectra show two different trends depending on the pressure and temperature conditions of the system. On the one hand, when the pressure is increased to 1.0 GPa while keeping the temperature at 300 K, the highly structured nature of Zn2+ second hydration shell is preserved. On the other hand, when the Zn2+ aqueous solution is simultaneously pressurized and heated to follow the melting curve above 1.0 GPa, the Zn2+ second shell loses its high degree of structuring and becomes much more disordered and unstructured. These results are confirmed by the analysis of MD simulations of Zn2+ aqueous solutions under high pressure. By combining distance and angular distribution functions it is possible to highlight the loss of water structuring in the Zn2+ second coordination shell that takes place upon pressurization and heating. A progressive crowding of the Zn2+ second shell is observed with increasing pressure; the water structure becomes remarkably different from that found at ambient conditions, and for pressure values higher than 1.0 GPa the tetrahedral arrangements of water molecules is highly distorted. Moreover, MD simulations of Zn2+ aqueous solutions performed at 1.0 GPa and at increasing temperature values have shown that the loss of water structuring in the Zn2+ second coordination shell observed by simultaneously pressurizing and heating is due to a combined effect of pressure and temperature, both producing an increase of the Zn2+ second-shell disorder. © 2017 American Chemical Society.