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Raman spectra of aqueous Ho 3+ , Er 3+ , Tm 3+ , Yb 3+ , and Lu 3+ -perchlorate solutions were measured over a large wavenumber range from 50-4180 cm -1 . In the low wavenumber range (terahertz region), strongly polarized Raman bands were detected at 387 cm -1 , 389 cm -1 , 391 cm -1 , 394 cm -1 , and 396 cm -1 , respectively, which are fairly broad (full widths at half height at ~52 cm -1 ). These isotropic Raman bands were assigned to the breathing modes, ν 1 Ln-O of the heavy rare earth (HRE) octaaqua ions, [Ln(H 2 O) 8 ] 3+ . The strong polarization of these bands (depolarization degree ~0) reveals their totally symmetric character. The vibrational isotope effect was measured in Yb(ClO 4 ) 3 solutions in H 2 O and D 2 O and the shift of the ν 1 mode in changing from H 2 O to D 2 O further supports the character of the band. The Ln-O bond distances of these HRE ions (Ho 3+ , Er 3+ , Tm 3+ , Yb 3+ , and Lu 3+ ) follow the order of Ho-O &gt; Er-O &gt; Tm-O &gt; Yb-O &gt; Lu-O which correlates inversely with the band positions of the breathing modes of their corresponding octaaqua ions [Ln(OH 2 ) 8 ] 3+ . Furthermore, the force constants, k Ln-O  , were calculated for these symmetric stretching modes. Ytterbium perchlorate solutions were measured over a broad concentration range, from 0.240 mol·L -1 to 2.423 mol·L -1 , and it was shown that with increasing solute concentration outer-sphere ion pairs and contact ion pairs were formed. At the dilute solution state (~0.3 mol·L -1 ), the fully hydrated ions [Yb(H 2 O) 8 ] 3+ exist, while at higher concentrations (C T &gt; 2 mol·L -1 ), ion pairs are formed. The concentration behavior of Yb(ClO 4 ) 3 (aq) shows similar behavior to the one observed for La(ClO 4 ) 3 (aq), Ce(ClO 4 ) 3 (aq) and Lu(ClO 4 ) 3 (aq) solutions. In ytterbium chloride solutions in water and heavy water, representative for the behavior of the other HRE ions, 1:1 chloro-complex formation was detected over the concentration range from 0.422-3.224 mol·L -1 . The 1:1 chloro-complex in YbCl 3 (aq) is very weak, diminishing rapidly with dilution and vanishing at a concentration &lt; 0.4 mol·L -1 .

On the Hydration of Heavy Rare Earth Ions: Ho3+, Er3+, Tm3+, Yb3+ and Lu3+—A Raman Study