Molecular dynamics simulations of Y(iii) coordination and hydration properties

Abstract

Y mainly exists in ionic rare-earth resources. During rare-earth carbonate precipitation, rare-earth ion loss in the precipitated rare-earth mother liquor often occurs due to CO₃²⁻ coordination and Y(III) hydration. Microscopic information on the coordination and hydration of CO₃²⁻ and H₂O to Y(III) has not yet been elucidated. Therefore, in this study, the macroscopic dissolution of Y(III) in different aqueous solutions of Na₂CO₃ was studied. The radial distribution function and coordination number of Y(III) by CO₃²⁻ and H₂O were systematically analyzed using molecular dynamics (MD) simulations to obtain the complex ion form of Y(III) in carbonate solutions. Density functional theory (DFT) was used to geometrically optimize and calculate the UV spectrum of Y(III) complex ions. This spectrum was then analyzed and compared with experimentally determined ultraviolet-visible spectra to verify the reliability of the MD simulation results. Results showed that Y(III) in aqueous solution exists in the form of [Y·3H₂O]³⁺ and that CO₃²⁻ is present in the bidentate coordination form. In 0–0.8 mol L⁻¹ CO₃²⁻ solutions, Y(III) was mainly present as the 5-coordinated complex [YCO₃·3H₂O]⁺. When the concentration of CO₃²⁻ was increased to 1.2 mol L⁻¹, [YCO₃·3H₂O]⁺ was converted into a 6-coordinated complex [Y(CO₃)₂·2H₂O]⁻. Further increases in CO₃²⁻ concentration promoted Y(III) dissolution in solution in the form of complex ions. These findings can be used to explain the problem of incomplete precipitation of rare earths in carbonate solutions.