Force Field Parameterization of Actinyl Molecular Cations Using the 12-6-4 Model.

Abstract

In this work, a set of 12-6-4 force fields (FFs) parameters were developed for the actinyl molecular cations, AnO2n+ (n = 1, 2), from uranium to plutonium for classical molecular dynamics (MD) for four water models: TIP3P, SPC/E, OPC3, and TIP4Pew. Such a non-bonded potential model taking into account the induced dipole between the metallic center and the surrounding molecules has shown better performances for various cations than the classic 12-6 non-bonded potentials. The parametrization method proposed elsewhere for metallic cations has been extended to these molecular cations. In contrast to the actinyl 12-6 FFs from the literature, the new models reproduce correctly both solvation and thermodynamic properties, thanks to the inclusion of the induced dipole term (C4). The transferability of such force fields was assessed by performing MD simulations of carbonato actinyl species, which are highly implicated in actinide migration or actinide extraction from seawater. A highly satisfying agreement was found when comparing the EXAFS signals computed from our MD simulation to the experimental ones. The set of FFs developed here opens new possibilities for the study of actinide chemistry.