First principles computational studies of spontaneous reduction reaction of Eu(III) in eutectic LiCl-KCl molten salt

Compared to Eu²⁺ the Eu³⁺ ion has a morerigid framework of the solvation shells, corroborating its stronger electrostatic interaction with neighboring ligands of Cl^- ions and a more favorable state on the aspect of enthalpy. Computations on vibrational frequency, however, pose significant contribution of vibrational entropy to the reaction Gibbs free energy for the reduction. Vibration frequency of Eu²⁺ is smaller than that of Eu³⁺, driving a more positive change of the entropy in the reduction reaction. Furthermore, an Eu²⁺ diffuses more quickly than an Eu³⁺ in the LiCl-KCl molten salt with switching mechanism of ligand Clions in the solvation shell. Our results propose that the spontaneity of the reduction reaction is driven by the entropic contribution by overcoming the penalty of the reaction enthalpy. We decoupled reaction Gibbs free energy into enthalpic and entropic contributions. The rigidity of the solvation shells was estimated by RDF, oxidation and coordination numbers, which largely described the enthalpic change