Molecular Dynamics Simulation Studies on Structure, Dynamics, and Thermodynamics of Uranyl Nitrate Solution at Various Acid Concentrations.

Abstract

The structural and dynamical characteristics of uranyl ions in an aqueous acidic environment are of immense importance in the field of nuclear fuel reprocessing. In view of that, the structural and dynamical behavior of the uranyl ion in water has been investigated by performing molecular dynamics (MD) simulations using different force fields. All the force fields have depicted similar structural and dynamical properties except the free energy of hydration where the Guilbaud-Wipff (GW) model performs well over the others. The calculated density using MD simulations is found to be in excellent agreement with the measured experimental density, which ensures the accuracy of the adopted GW force field. The calculated surface tension and shear viscosity are seen to be increased with uranyl nitrate concentrations. At a higher concentration of about 4.0 mol/L, the supersaturation effect has been captured by an inflection in the plot of surface tension and shear viscosity against concentration because of the solution heterogeneity, which was correlated by an inflection in the scattering intensity observed by performing the dynamic light scattering experiment. The binding mode of nitrate ions with the uranyl ion is found to be concentration-dependent, and at higher concentration, it is predominantly monodentate.