Hydration and ion pair formation in common aqueous La(III) salt solutions--a Raman scattering and DFT study

Raman spectra of aqueous lanthanum perchlorate, triflate (trifluorosulfonate), chloride and nitrate solutions were measured over a broad concentration (0.121-3.050 mol L(-1)) range at room temperature (23 °C). A very weak mode at 343 cm(-1) with a full width at half height at 49 cm(-1) in the isotropic spectrum suggests that the nona-aqua La(III) ion is thermodynamically stable in dilute perchlorate solutions (∼0.2 mol L(-1)) while in concentrated perchlorate solutions outer-sphere ion pairs and contact ion pairs are formed. The La(3+) nona-hydrate was also detected in a 1.2 mol L(-1) La(CF3SO3)3(aq). In lanthanum chloride solutions chloro-complex formation was detected over the measured concentration range from 0.5-3.050 mol L(-1). The chloro-complexes in LaCl3(aq) are fairly weak and disappear with dilution. At a concentration <0.1 mol L(-1) almost all complexes disappeared. In LaCl3 solutions, with additional HCl, a series of chloro-complexes of the type [La(OH2)(9-n)Cln](+3-n) (n = 1-3) were formed. The La(NO3)3(aq) spectra were compared with a spectrum of a 0.409 mol L(-1) NaNO3(aq) and it was concluded that in La(NO3)3(aq) over the concentration range from 0.121-1.844 mol L(-1), nitrato-complexes, [La(OH2)(9-n)(NO3)n](+3-n) (n = 1, 2) were formed. These nitrato-complexes are quite weak and disappear with dilution <0.01 mol L(-1). DFT geometry optimizations and frequency calculations are reported for a lanthanum-nona-hydrate with a polarizable dielectric continuum in order to take the solvent into account. The bond distances and angles for the cluster geometry of [La(OH2)9](3+) with the polarizable dielectric continuum are in good agreement with data from recent structural experimental measurements and high quality simulations. The DFT frequency of the La-O stretching mode at 328.2 cm(-1), is only slightly smaller than the experimental one.