Quantum Mechanical and Molecular Dynamical Simulations on Thorium(IV) Hydrates in Aqueous Solution

Citations Over TimeTop 11% of 2001 papers

Abstract

We report the combined quantum mechanical and molecular dynamical simulations on thorium(IV) hydrates in aqueous solution. Hydration of the Th4+ ion in aqueous system was first investigated using the B3LYP hybrid density functional theoretical calculations. The results show that the first shell hydration number of Th4+ ion in liquid phase is 9 at the bond distance of Th−OI 2.54(1) Å and Th−HI 3.22(1) Å. Second, the second shell hydration properties of the Th4+ ion in aqueous solution were studied by the molecular dynamical simulation using AMBER force field. The concept of the hydrated ion was used, [Th(H2O)9]4+ being the cationic entity interacting in solution. The [Th(H2O)9]4+−water interaction potential was developed by ab intio B3LYP calculations. The partial atomic charge of [Th(H2O)9]4+ is derived from the ESP method. The MD calculated results show a well-defined second coordination shell and an ill-defined third shell around the [Th(H2O)9]4+ ion. The strong hydrogen bonding due to the polarization of the first coordination sphere water molecules leads to a mean coordination number of 18.9 water molecules in the second shell at the bond distance of Th−OII 4.75 Å and Th−HII 5.35 Å. The residence time of a water molecule in the second hydration shell is 423.4 ps. Our simulated results indicate that the hydrated ion concept for simulating the Th4+ ion in aqueous solution is appropriate.

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