A new set of ionic radii in aqueous solution has been derived for lanthanoid(III) cations starting from a very accurate experimental determination of the ion-water distances obtained from extended X-ray absorption fine structure (EXAFS) data. At variance with previous results, a very regular trend has been obtained, as expected for this series of elements. A general procedure to compute ionic radii in solution by combining the EXAFS technique and molecular dynamics (MD) structural data has been developed. This method can be applied to other ions allowing one to determine ionic radii in solution with an accuracy comparable to that of the Shannon crystal ionic radii.

In this work we have extended our previously presented polarizable pair interaction potential for La(3+)-water [Duvail et al., J. Chem. Phys. 127, 034503 (2007)] to the whole lanthanoid(III) series (Ln(3+)) interacting with water. This was performed taking into account known modification of ionic radius and atomic polarizability across the series and thus changing potential parameters according to that. Our procedure avoids the hard task of doing expensive high level ab initio calculations for all the atoms in the series and provides results in good agreement with experimental data and with ab initio calculations performed on the last atom in the series (Lu(3+), the atom for which the extrapolation should be in principle much crude). Thus we have studied the hydration properties of the whole Ln(3+) series by performing classical molecular dynamics in liquid phase. This systematic study allows us to rationalize from a microscopic point of view the different experimental results on Ln(3+)-water distances, first shell coordination numbers and first shell water self-exchange reactivity. In particular, we found that across the series the coordination number decreases from 9 for light lanthanoids to 8 for heavy lanthanoids in a continuous shape. This is due to the continuous changing in relative stability of the two forms that can be both populated at finite temperature with different probabilities as a function of the Ln(3+) atomic number. The changeover of the Ln(3+) ionic radius across the series resulted to be the main driving physical properties governing not always the Ln(3+)-water distance changing across the series but also the observed coordination number and consequently ligand dynamics.

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Pair interaction potentials (IPs) were defined to describe the La(3+)-OH(2) interaction for simulating the La(3+) hydration in aqueous solution. La(3+)-OH(2) IPs are taken from the literature or parametrized essentially to reproduce ab initio calculations at the second-order Moller-Plesset level of theory on La(H(2)O)(8) (3+). The IPs are compared and used with molecular dynamics (MD) including explicit polarization, periodic boundary conditions of La(H(2)O)(216) (3+) boxes, and TIP3P water model modified to include explicit polarization. As expected, explicit polarization is crucial for obtaining both correct La-O distances (r(La-O)) and La(3+) coordination number (CN). Including polarization also modifies hydration structure up to the second hydration shell and decreases the number of water exchanges between the La(3+) first and second hydration shells. r(La-O) ((1))=2.52 A and CN((1))=9.02 are obtained here for our best potential. These values are in good agreement with experimental data. The tested La-O IPs appear to essentially account for the La-O short distance repulsion. As a consequence, we propose that most of the multibody effects are correctly described by the explicit polarization contributions even in the first La(3+) hydration shell. The MD simulation results are slightly improved by adding a-typically negative 1r(6)-slightly attractive contribution to the-typically exponential-repulsive term of the La-O IP. Mean residence times are obtained from MD simulations for a water molecule in the first (1082 ps) and second (7.6 ps) hydration shells of La(3+). The corresponding water exchange is a concerted mechanism: a water molecule leaving La(H(2)O)(9) (3+) in the opposite direction to the incoming water molecule. La(H(2)O)(9) (3+) has a slightly distorded "6+3" tricapped trigonal prism D(3h) structure, and the weakest bonding is in the medium triangle, where water exchanges take place.

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In this work, we have developed a polarizable classical interaction potential to study actinoids(III) in liquid water. This potential has the same analytical form as was recently used for lanthanoid(III) hydration [M. Duvail, P. Vitorge, and R. Spezia, J. Chem. Phys. 130, 104501 (2009)]. The hydration structure obtained with this potential is in good agreement with the experimentally measured ion-water distances and coordination numbers for the first half of the actinoid series. In particular, the almost linearly decreasing water-ion distance found experimentally is replicated within the calculations, in agreement with the actinoid contraction behavior. We also studied the hydration of the last part of the series, for which no structural experimental data are available, which allows us to provide some predictive insights on these ions. In particular we found that the ion-water distance decreases almost linearly across the series with a smooth decrease of coordination number from nine to eight at the end.

Published liquid-liquid extraction studies of Pa(V) were interpreted with aqueous mono-, di-and trications. B3LYP DFT is applied here to such cations surrounded by two explicit hydration layers: Linear or tetrahedral geometries are found for the Pa(V) aquo ions. PaO 2 + is similar to the other AnO 2 + cations, but has strong apical bonds, resulting from the highly negative O yl charge, which decreases along the An(V) series. This explains the instability of PaO 2 + in water, and the differences with the heavier An(V). PaO 2 + diprotonates to give Pa(OH) 2 3+ and can further dihydrolyse to give T d -Pa(OH) 4 + , which might very well be the most stable Pa(V) monocation. PaOOH 2+ is confirmed to be the Pa(V) aqueous dication invoked in the literature for pH r 1.4 AE 0.7. PaO 3+ is confirmed in sulfate solution, with a bond length close to 180 pm. Pa(OH) 2 3+ cannot be excluded in other conditions. The strong influence of the solvent was not fully taken into account in most previous theoretical studies that focused only on bare or partially solvated PaO 2 + . Toraishi et al. have studied hydrated Pa(V) and our work confirms this study and its qualitative interpretation. The new tetrahedral Pa(OH) 4 + geometry that is shown here to be important opens the field to further quantum chemical studies of Pa(V) and other f-elements. As a test for the two-shell model approach for Pa(V), fluoride coordination to Pa(V) is studied and compared with published EXAFS data: an excellent fit is obtained with the well-established species PaF 7 2À , but most other stoichiometries tested are precluded.