Issue 16, 2003

Solvation of M3+ lanthanide cations in room-temperature ionic liquids. A molecular dynamics investigation

Abstract

We report a molecular dynamics study of the solvation of M3+ lanthanide cations (La3+, Eu3+ and Yb3+) in two room-temperature ionic liquids: [BMI][PF6] based on 1-butyl-3-methyl-imidazolium+,PF6 and [EMI][TCA] based on 1-ethyl-3-methyl-imidazolium+,AlCl4. They reveal specific solvation as a function of the cation size and on the solvent. In [BMI][PF6] solution, the three studied M3+ cations are surrounded by six PF6 anions, while in [EMI][TCA] solution, they are surrounded by eight AlCl4 anions. The precise binding mode of the AlCl4 or PF6 solvent anions (denticity, number of coordinated halides and dynamics) depends on the M3+ cation size. The first shell PF6 anions rotate markedly during the dynamics while AlCl4 do not. In both liquids, this first ionic shell is surrounded by about 11–13 imidazolium cations. The solvation of the neutralizing NO3 counterions is similar in both liquids, and involves mainly imidazolium+ cations in the first shell (≈5.0 in [BMI][PF6] and 4.3 in [EMI][TCA]). When simulated in the gas phase, the first anionic shells are similar, but more rigid than in the solutions. Finally, free energy calculations are performed to compare the Eu3+/La3+ and Yb3+/Eu3+ solvation. In both ionic liquids, the smaller cations are better solvated, but the differences from one cation to the other are weaker than in water.

Supplementary files

Article information

Article type
Paper
Submitted
08 May 2003
Accepted
20 Jun 2003
First published
07 Jul 2003

Phys. Chem. Chem. Phys., 2003,5, 3481-3488

Solvation of M3+ lanthanide cations in room-temperature ionic liquids. A molecular dynamics investigation

A. Chaumont and G. Wipff, Phys. Chem. Chem. Phys., 2003, 5, 3481 DOI: 10.1039/B305091B

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