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Relativistic Quantum Chemistry Applied to Actinides

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Relativistic Quantum Chemistry Applied to Actinides Relativistic Quantum Chemistry Applied to Actinides by Samuel Omonigho Odoh A Thesis submitted to the Faculty of Graduate Studies of The University of Manitoba in partial fulfillment of the requirements of the degree of DOCTOR OF PHILOSOPHY Department of Chemistry University of Manitoba Winnipeg, Canada Copyright © 2012 by Samuel O. Odoh Table of Contents Table of Contents ………………………………………………………………………………...i List of Figures ……………………………………………………………………………….......iv List of Tables ……………………………………………………………...…………………….xi List of Abbreviations …………………………………………………………………………..xvii Abstract …………………………………………………………………….…………………..xix Acknowledgement ……………………………………………………………………………..xxi Chapter 1- Introduction ……………………………………………..………….………………...1 1.1. The Actinide Elements and their Uses ……………………………….…….………………..1 1.2. Chemical Properties of Actinides ……………...………………..…………………………..4 1.3. Theoretical Studies of Actinide Complexes ….…………………..…………………….…...9 1.3.1. The Schrödinger Equation ….…………………..………………..…………….………….9 1.3.2. The Variational Principle and Electronic Basis Sets….………….……………………….10 1.3.3. The Hartree-Fock Method and Post Hartree-Fock Approaches …..…………...…………13 1.3.4. Density Functional Theory ….…………………………………….………….…………..17 1.3.5. Relativistic Effects ….……………………………….……………….…………………..21 1.3.6. Solvation Effects ….………………………………….…………….…………………….25 i 1.4. Organization of this Thesis ….……………………………………….……..……………...26 1.5. References ....…….…………………………...…….……………………....……………....29 Chapter 2- Performance of Relativistic Effective Core Potentials for DFT Calculations on Actinide Compounds ….……………………………………….……………….………………36 Chapter 3- Theoretical Study of the Structural Properties of Plutonium IV and VI Complexes ….……………………………………….……………………………………….……………...64 Chapter 4- Theoretical Study of the Structural and Electronic Properties of Plutonyl Hydroxides ….……………………………………….………………………………………………………98 - - 2- - Chapter 5- DFT Study of Uranyl Peroxo Complexes with H2O, F , OH , CO3 and NO3 ….151 Chapter 6- Theoretical Study of the Reduction of Uranium(VI) Aquo Complexes on Titania Particles and by Alcohols …………………….……….………..……………………………...195 Chapter 7- QM and QM/MM Study of Uranyl Fluorides in the Gas Phase, Aqueous Phase and in the Hydrophobic Cavities of Tetrabrachion …………………………………………………...231 Chapter 8- Novel and Stable U(V)/U(V) Binuclear Complexes Formed by Oxo-functionalization of Axial Oxo Atoms …………………………………………………………………………..269 Chapter 9- Theoretical Study of a Gas-Phase Binuclear Uranyl Hydroxo Complex, - [(UO2)2(OH)5] …………………………….………………………………………………….295 Chapter 10- Summary and Future Studies of Actinide Complexes …………………………..325 10.1. Summary ………………………………………………………………………………...325 ii 10.2. Future Studies of Actinide Complexes Specific to this Thesis …………..……………...328 10.3. General Directions for Computational Studies of Actinide Complexes ………………...330 References ……………….……………….……………….……………….…………………..331 List of Publications ……………………………………………………………………………336 iii List of Figures Figure 1.1: The actinides in the periodic table of elements ……………………………..……….2 Figure 1.2: The aquo complexes of U(VI) and U(IV) …………………………………..………8 Figure 1.3: Schematic description of the chapters in this thesis ………………………….…….28 Figure 2.1: Absolute Deviations of the Vibrational Wavenumbers, cm-1 for NUN, NUO+ and CUO computed using Stuttgart RECPs with the aug-cc-pVTZ ligand basis set and the AE four- component method with the L2 basis set ………………………………………………….…...44 Figure 2.2: Distorted Planar T-Shaped Structure of UO3(g) ……………………………….…..46 -1 Figure 2.3: Absolute Deviations of the Vibrational Wavenumbers, cm , for UO3 and UF6 computed using Stuttgart RECPs with the aug-cc-pVTZ ligand basis set and the AE four- component method with the L2 basis set ………………………………………………….…..50 Figure 2.4: Absolute Deviations of the Enthalpy Changes, kJ/mol for Reactions 1-5 computed using Stuttgart RECPs with the aug-cc-pVTZ ligand basis set and the AE four-component method …………………………………………………………………………………….…...55 2+ Figure 3.1: (Left) The An=Oyl bond lengths (Å) in the bare actinyl moieties, AnO2 as well as 2+ the An=Oyl and average An-OH2 bond lengths (Å) in the pentaaquo complexes, [AnO2(H2O)5] . (Right) The actinyl symmetric and asymmetric stretching vibrational frequencies (cm-1) in the 2+ 2+ bare actinyl moieties, AnO2 and the pentaaquo complexes, [AnO2(H2O)5] . ………….…...74 1+ Figure 3.2: (Left) The An=Oyl bond lengths (Å) in the bare actinyl moieties, AnO2 as well as the An=Oyl bond lengths and average An-OH2 bond lengths (Å) in the pentaaquo complexes, iv 1+ [AnO2(H2O)5] . (Right) The actinyl symmetric and asymmetric stretching vibrational -1 1+ frequencies (cm ) in the bare actinyl moieties, AnO2 and the pentaaquo complexes, 1+ [AnO2(H2O)5] . These values were obtained with the obtained using the PBE functional and PCM solvation model ……………………………………………………………………….….75 Figure 3.3: A. The cis (top) and trans (bottom) isomers of the PuO2Cl2(H2O)2 complex. B. The cis (top) and trans (bottom) isomers of the PuO2Cl2(H2O)3 complex …………………………80 + Figure 3.4: A) The decrease in the An=Oyl and An-Cl bond lengths (Å) on addition of 2Cs to the 2- -1 [AnO2Cl4] complexes. B) The increase in the actinyl stretching vibrational frequencies (cm ) + 2- on addition of 2Cs to the [AnO2Cl4] complexes …………………………………………….81 Figure 3.5: The optimized structure of plutonyl diaquo-dinitrate, PuO2(NO3)2(H2O)2 obtained using the B3LYP functional ……………………………………………………………………85 4+ Figure 3.6: The optimized structures of several plutonium (IV) complexes: A) Pu(H2O)8 , B) 2+ 2- Pu(NO3)2 , C) Pu(NO3)4(H2O)3 and D) Pu(NO3)6 calculated with the B3LYP functional in the aqueous phase …………………………………………………………………………………..89 2-n Figure 4.1: Optimized structures of the aquo-hydroxo [PuO2(H2O)5-n(OH)n] complexes obtained at the BP86/B2 level with the COSMO solvation model ……………..……….……105 2-n Figure 4.2: Optimized structures of the aquo-hydroxo [PuO2(H2O)4-n(OH)n] complexes obtained at the BP86/B2 level with the COSMO solvation model …………………………...106 Figure 4.3: Optimized structures of the bis-plutonyl aquo tetrahydroxo and dihydroxo complexes obtained at the B3LYP/B3 level in the gas phase …………...………………………………..114 v + Figure 4.4: Structures of [(PuO2)3(H2O)6(O)(OH)3] obtained at the BP86/B2/COSMO level. The C3V structure is shown on the left while the structure with a bridging aquo group is shown on the right ……………………………………………………………………………………………115 Figure 4.5: Scheme depicting the formation and decomposition of the μ3-oxo hexagonal trimetallic core of the trimer aquo-hydroxo complexes ………….…………………………....127 2+ Figure 4.6: The molecular orbitals of [PuO2] ...…………….……..……………...………....129 2+ Figure 4.7: The energy levels of the [AnO2] optimized at the BP86/B2 level with the COSMO model ………………………………………………………………………………………….130 2- Figure 4.8: Selected occupied alpha spin MOs of [PuO2(OH)4] ……………………..……..132 2+ Figure 4.9: The energy levels of the [AnO2(OH)4] optimized at the BP86/B2 level with the COSMO model ……………………………………………….……………………………….134 2+ Figure 4.10: The 39th to 62nd MOs of [(PuO2)2(OH)2] of alpha spin ……………..……….136 + Figure 4.11: Selected alpha spin MOs of the trimer complex, [(PuO2)3(O)(OH)3] …..……...139 + Figure 4.12: Abbreviated energy level diagram of the [(AnO2)3(O)(OH)3] complexes ……...142 2+ Figure 5.1: The structures of UO2 and its peroxo derivatives optimized at the B3LYP/B1 level in aqueous solution ……………………………………….………………...…………………156 Figure 5.2: The molecular orbitals of UO2(O2). The geometry of this complex was optimized with the PCM approach and the B3LYP functional ………………………………………….159 vi 2+ Figure 5.3: Simulated IR spectra of UO2 and its peroxo derivatives obtained at the at the B3LYP/B1 level in aqueous solution ………………………………………………………….160 2- Figure 5.4: MO-26 and MO-27 of the C2v structure of UO2(O2)2 ………………………….163 2+ Figure 5.5: The structures of UO2(H2O)5 and its peroxo derivatives optimized at the B3LYP/B1 level in aqueous solution ………………………………………………………………………166 2- Figure 5.6: The structures of UO2F4 and its peroxo derivatives optimized at the B3LYP/B1 level in aqueous solution ………………………………………………………………………170 2- Figure 5.7: The structures of UO2(OH)4 and its peroxo derivatives optimized at the B3LYP/B1 level in aqueous solution ………….……………………………………...……………………173 4- Figure 5.8: MO-30 of cis and trans- UO2(O2)2(OH)2 ………….………..…………………..176 4- Figure 5.9: The structures of UO2(CO3)3 and its peroxo derivatives optimized at the B3LYP/B1 level in aqueous solution ……………………………………………………………………....178 Figure 6.1: Possibilities for charge transfer to U(VI) complexes adsorbed on TiO2 crystals or nanoparticles …………………………………………………………………………………..199 2+ Figure 6.2: Structure of UO2 adsorbed at the rutile (110) surface at the bridging oxygen atoms …………………………...............…………………………………………………………….204 Figure 6.3: Total and partial electronic density of states (DOS) obtained for a clean rutile (110) slab while using with the PBE functional (left) and the PBE+U approach (right, U=4.2 eV) …………………………………………………………………………………………………206 vii Figure 6.4: Total and partial electronic density of states (DOS) obtained for hydroxylated rutile (110) slabs with the PBE+U approach (U=4.2 eV for Ti 3d and U=4.0 eV for U 5f) ……………………………………….………………………………………………………...207 Figure 6.5: Total and partial electronic density of states (DOS) obtained for rutile (110) slabs 2+ with an adsorbed UO2 group obtained with the PBE+U approach (U=4.2 eV for Ti-3d and U=4.0 eV for U-5f)….………………………………………………………………………...210 Figure 6.6: Total and partial electronic density of
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