The ion association behavior in aqueous lanthanum sulfate solutions was investigated using density functional theory (DFT). The structures and properties of [La(SO4)m·(H2O)n](3-2m) clusters, where m = 1 to 3 and n = 1 to 9, were examined at the PBE0/6-311+G(d, p) level. The results show that Lanthanum sulfate hydrated clusters exist in the aqueous solution's microscopic state of contact ion pairs (CIP). [La(SO4)(H2O)n]+ and [La(SO4)2·(H2O)n]-, and [La(SO4)3·(H2O)n]3- clusters approximately reach the saturation of the first water shell at n = 7 and 6 and 3. [La(SO4)2·(H2O)6]- and [La(SO4)3·(H2O)3]3- clusters have lower binding energy than [LaSO4·(H2O)n]+. This indicates that lanthanum sulfate tends to aggregate in an aqueous solution. Compared to the gas-phase cluster structures, the distance of R(La-O)H2O expands in the PCM solvent model, while R(La-O)SO4 contracts. The hydration energy of LaSO4·(H2O)7, La(SO4)2·(H2O)6, and La(SO4)3·(H2O)3 were -76.5, -54.1 and -332.0 kcal/mol, respectively. The molecular dynamics simulation results show that La is more inclined to coordinate with sulfate's oxygen than water's oxygen, and the coordination number of water around La3+ is 6.075. These results are consistent with the calculated results by DFT.
Keywords: Density functional theory; Ion association; Lanthanum sulfate hydrated clusters; Molecular dynamics.
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