RESUMEN
Lanthanides are widely assumed not to form covalent bonds due to the localized nature of their 4f valence electrons. This work demonstrates that the ionic bond of Sm(II) with cyclononatetraenyl (η9-C9H9-) in [Sm(η9-C9H9)2] can be modulated and becomes more covalent by photon-induced transfer of Sm 4f electrons to Sm 5d orbitals. This photon-induced change in bonding properties facilitates a subsequent reconfiguration of [Sm(η9-C9H9)2]. As a result, Sm-C bond length contraction is detected and the local Sm coordination environment exhibits more extensive disorder. Both Sm 4f and 5d electrons have increased participation in covalent Sm-ligand interactions. The Sm L3-edge valence band resonant inelastic X-ray scattering (VB-RIXS), high-resolution X-ray absorption near-edge structure (HR-XANES), and quantum chemical computations showcase a spectroscopic methodology for in-depth studies of bond covalency of lanthanide atoms.
RESUMEN
The solubility of 99Tc(iv) was investigated in dilute to concentrated carbonate solutions (0.01 M ≤ Ctot≤ 1.0 M, with Ctot = [HCO3-] + [CO32-]) under systematic variation of ionic strength (I = 0.3-5.0 M NaHCO3-Na2CO3-NaCl-NaOH) and pHm (-log[H+] = 8.5-14.5). Strongly reducing conditions (pe + pHm≈ 2) were set with Sn(ii). Carbonate enhances the solubility of Tc(iv) in alkaline conditions by up to 3.5 log10-units compared to carbonate-free systems. Solvent extraction and XANES confirmed that Tc was kept as +IV during the timeframe of the experiments (≤ 650 days). Solid phase characterization performed by XAFS, XRD, SEM-EDS, chemical analysis and TG-DTA confirmed that TcO2·0.6H2O(am) controls the solubility of Tc(iv) under the conditions investigated. Slope analysis of the solubility data in combination with solid/aqueous phase characterization and DFT calculations indicate the predominance of the species Tc(OH)3CO3- at pHm≤ 11 and Ctot≥ 0.01 M, for which thermodynamic and activity models are derived. Solubility data obtained above pHm≈ 11 indicates the formation of previously unreported Tc(iv)-carbonate species, possibly Tc(OH)4CO32-, although the likely formation of additional complexes prevents deriving a thermodynamic model valid for this pHm-region. This work provides the most comprehensive thermodynamic dataset available for the system Tc4+-Na+-Cl--OH--HCO3--CO32--H2O(l) valid under a range of conditions relevant for nuclear waste disposal.
RESUMEN
The pressure-induced phase transition sequence in PbSc(0.5)Ta(0.5)O(3) (PST) and PbSc(0.5)Nb(0.5)O(3) (PSN) heavily doped with homo- and heterovalent cations on the A- or B-site of the perovskite-type structure (ABO(3)) was analysed by in situ synchrotron x-ray diffraction and Raman spectroscopy up to pressures of 25 GPa. We focused on the structural phenomena occurring above the first pressure-induced phase transition at p(c1) from a relaxor state to a non-polar rhombohedral phase with antiphase tilting of the BO(6) octahedra. The samples studied were PST doped with Nb(5+) and Sn(4+) on the B-site, PST doped with Ba(2+) and La(3+) on the A-site and PSN doped with Sr(2+) and La(3+) on the A-site. All of them exhibit a second pressure-induced phase transition at p(c2), similar to pure PST and PSN. The second transition involves the development of either order of antiparallel Pb(2+) displacements and complementary a(+)b(-)b(-) octahedral tilts, or a(-)b(-)b(-) (0 ≤ a < b) tilting alone. As in pure PST and PSN, the second phase transition is preceded by the occurrence of unequal octahedral tilts on the local scale. The substitution of Nb(5+) for Ta(5+) as well as the coupled substitution of Sn(4+) for Sc(3+) + Ta(5+) on the octahedral B sites increases the second critical pressure. The doping by Nb(5+) also reduces the length of coherence of antipolar Pb(2+) order developed at p(c2). The isovalent substitution of the larger Ba(2+) for Pb(2+) on the A-site suppresses the antipolar Pb(2+) order due to the induced local elastic stresses and thus significantly increases p(c2). The substitution of smaller cations for Pb(2+) on the A-site generally favours the development of long-range order of antiparallel Pb(2+) displacements because of the chemically enhanced a(-)a(-)a(-) octahedral tilts. However, this ordering is less when the dopant is aliovalent, due to the charge imbalance on the A-site. For all of the relaxors studied here, the dynamic compressibility estimated from the pressure derivative of the wavenumber of the soft mode associated with the first phase transition is larger in the pressure interval between p(c1) and p(c2) than above p(c2). The dynamic compressibility of the phase above p(c2) decreases if the antipolar Pb(2+) order is disturbed.