Development and application of effective pairwise potentials for UO2n+, NpO2n+, PuO2n+, and AmO2n+ (n = 1, 2) ions with water

Abstract

Intra- and intermolecular force field parameters for the interaction of actinyl ions (AnO₂ⁿ⁺, where, An = U, Np, Pu, Am and n = 1, 2) with water have been developed using quantum mechanical calculations. Water was modeled with the extended simple point charge potential (SPC/E). The resulting force field consists of a simple form in which intermolecular interactions are modeled with pairwise Lennard-Jones functions plus partial charge terms. Intramolecular bond stretching and angle bending are treated with harmonic functions. The new potentials were used to carry out extensive molecular dynamics simulations for each hydrated ion. Computed bond lengths, bond angles and coordination numbers agree well with known values and previous simulations. Hydration free energies, computed from molecular dynamics simulations as well as from quantum simulations with a solvation model, were in reasonable agreement with estimated experimental values.