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In-Plane Cation Ordering and Sodium Displacements in Layered Honeycomb Oxides with Tetravalent Lanth
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Understanding the Interplay of Vacancy, Cation, and Charge Ordering in the Tunable Sc[subscript 2]VO
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Emergence of A-Site Cation Order in the Small Rare-Earth Melilites SrREGa[subscript 3]O[subscript 7]
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Trivalent Cations Slow Electron Transfer to Macrocyclic Heterobimetallic Complexes
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Guided Ion Beam and Quantum Chemical Investigation of the Thermochemistry of Thorium Dioxide Cations: Thermodynamic Evidence for Participation of f Orbitals in Bonding
Kinetic energy dependent reactions of ThO + with O 2 are studied using a guided ion beam tandem mass spectrometer. The formation of ThO 2 + in the reaction of ThO + with O 2 is observed to be slightly endothermic and also exhibits two obvious features in the cross section. These kinetic energy dependent cross sections were modeled to determine a 0 K bond dissociation energy of D 0 (OTh + - O) = 4.94 ± 0.06 eV. This value is slightly larger but within experimental uncertainty of less precise previously reported experimental values. The higher energy feature in the ThO 2 + cross section was also analyzed and suggests formation of an excited state of the product ion lying 3.1 ± 0.2 eV above the ground state. Additionally, the thermochemistry of ThO 2 + was explored by quantum chemical calculations, including a full Feller-Peterson-Dixon (FPD) composite approach with correlation contributions up to CCSDT(Q) and four-component spin-orbit corrections, as well as more approximate CCSD(T) calculations including semiempirical estimates of spin-orbit energy contributions. The FPD approach predicts D 0 (OTh + -O) = 4.87 ± 0.04 eV, in good agreement with the experimental value. Analogous FPD results for ThO+, ThO, and ThO 2 are also presented, including ionization energies for both ThO and ThO 2 . The ThO 2 + bond energy is larger than those of its transition metal congeners, TiO 2 + and ZrO 2 + , which can be attributed partially to an actinide contraction, but also to contributions from the participation of f orbitals on thorium that are unavailable to the transition metal systems.
A Computational Assessment of Actinide Dioxide Cations AnO 2 2+ for An = U to Lr: The Limited Stability Range of the Hexavalent Actinyl Moiety, [O=An=O] 2+
The isolated gas-phase actinide dioxide dications, AnO 2 2+ , were evaluated by DFT and coupled cluster CCSD(T) calculations for 12 actinides, An = U–Lr. CASSCF calculations were used to define the orbitals for the CCSD(T) calculations. The characteristic linear [O$=$An$=$O] 2+ hexavalent actinyl(VI) was found to be the lowest energy structure for An = U, Np, and Pu, which also form stable actinyl(VI) species in solution and possibly for Am when spin–orbit effects are included. For Am, there is a divalent [An II (O 2 )] 2+ structure where the dioxygen is an end-on physisorbed η 1 - 3 O 2 2 kcal/mol above the actinyl when spin–orbit effects are included which lower the energy of the actinyl structure. For An = Cm, Bk, and Lr, the lowest energy structure is trivalent [An III (O 2 – )] 2+ where the dioxygen is a side-on superoxide, η 2 -O 2 – . For Cm, the actinyl is close in energy to the ground state when spin–orbit effects are included. For An = Cf, Es, Fm, Md, and No, the lowest energy structure is divalent [An II (O 2 )] 2+ where the dioxygen is an end-on physisorbed η 1 - 3 O 2 . The relative energies suggest that curyl(VI) and berkelyl(VI), like well-known americyl(VI), might be stabilized by coordinating ligands in condensed phases. The results further indicate that for californyl and beyond, the actinyl(VI) moieties will probably be elusive even using strong donor ligands. The prevalence of low oxidation states (OSs) An(II) and An(III) for transplutonium actinides reflects stabilization of the 5f orbitals and validates established trends, including the remarkably high stability of divalent No. Finally, bond distances and other parameters suggest maximum bond covalency around plutonyl(VI), with a particularly substantial decrease in bond strength between americyl(VI) and curyl(VI).
Cation-π Complexes of Silver Studied with Photodissociation and Velocity-Map Imaging
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Electronic Structure of Superoxidized Radical Cationic Dodecaborate-Based Clusters
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Photodissociation and Infrared Spectroscopy of Uranium–Nitrogen Cation Complexes
Laser vaporization of uranium in a pulsed supersonic expansion of nitrogen is used to produce complexes of the form U + (N 2 ) n (n = 1–8). These ions are mass selected in a reflectron time-of-flight spectrometer and studied with visible and UV laser fixed-frequency photodissociation and with tunable infrared laser photodissociation spectroscopy. The dissociation patterns and spectroscopy of U + (N 2 ) n indicate that N 2 ligands are intact molecules and that there is no insertion chemistry resulting in UN + or NUN + . Fixed frequency photodissociation at 532 and 355 nm indicate that the U + –N 2 bond dissociation energy varies little with changing coordination. The photon energy and the number of ligands eliminated allow an estimate of the average U + –N 2 dissociation energy of 12 kcal/mol. Infrared bands are observed for these complexes near the N–N stretch vibration via elimination of N 2 molecules. These resonances are observed to be shifted about 130 cm–1 to the red from the free-N 2 frequency for complexes with n = 3–8. Density functional theory indicates that U + is most stable in the sextet state in these complexes and that N 2 molecules bind in end-on configurations. Furthermore, the fully coordinated complex is predicted to be U + (N 2 ) 8 , which has a cubic structure. The vibrational frequencies predicted by theory are consistently lower than those in the experiment, independent of the isomeric structure or spin state of the complexes. Despite its failure to reproduce the infrared spectra, theory provides an average U + –N 2 dissociation energy of 11.8 ± 0.5 kcal/mol, in good agreement with the value from the experiments.
Structures and Energetics of E 2 H 3 + (E = As, Sb, and Bi) Cations
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