Polarizable force field parameterization and theoretical simulations of ThCl4 -LiCl molten salts.

Abstract

Recycle of thorium is an essential process in the thorium-uranium closed fuel cycle of molten salt reactor (MSR). Pyrochemical treatment of spent nuclear fuel using chloride molten salts as medium has been considered as a promising method. In this article, we performed molecular dynamics simulations on the ThCl4 LiCl molten salts using a polarizable force field parameterized by us from first-principles calculations. The microscopic structures and macroscopic properties at different compositions were investigated using the developed force field to understand the structure/property relationship in the mixture. The differences between ThCl4 LiCl and ThF4 LiF MSs are compared to understand the behaviors of Th4+ in the fluoride-chloride mixed media. In the molten fluorides, the coordination number of Th4+ is larger, and the resulting more shared anions lead to lower ThF dissociation barrier and shorter lifetime of the Th4+ first solvation shell. Our results also indicate the Pauling's structural rules for crystals can be used to rationalize the local structures in molten salts. © 2018 Wiley Periodicals, Inc.