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$il\VOLVEMENT OF RETII\OIC ACID II{ - MSpace at the University of ...$

PBE Perdew, Burke and Ernzerhof (GGA method) PCM polarized continuum model PUREX Plutonium Uranium Recovery by Extraction RECP relativistic effective–core potential RI resolution of identity redox reduction–oxidation (potential) SAS solvent accessible surface SC–ECP small core effective core potential (relativistic method) SCF self-consistent field SCM Scientific Computing & Modelling SCRF self-consistent reaction field STO Slater–type orbital SVWN Slater exchange functional combined with Vosko, Wilk and Nusair correlation functional (GGA method) THF or thf tetrahydrofuran (solvent) TM transition metal TZP triple zeta polarized (basis set) TZVP triple zeta valence polarized (basis set) VDZ valence double zeta (basis set) VTZ valence triple zeta (basis set) XC exchange–correlation (potential) ZORA zero order relativistic approximation (relativistic method) ZPE zero-point energy (correction) xvi
1.1 Motivation CHAPTER ONE INTRODUCTION The ongoing proliferation of fissile material worldwide, whether for the purposes of being used for nuclear weapons or nuclear power generation has created a genuine cause for anxiety regarding the immediate and long-term global consequences to both personal health and the environment. As a result, the radioactive waste and groundwater contamination created by six decades of atomic weapons production and nuclear power generation, has made the chemistry of the early actinides (An = U, Np, Pu, Am) and actinyls AnO2 n+ (n = 1 or 2) related to one of the most pressing environmental challenges of our time. Cause for concern exists should certain actinides in radioactive wastes be introduced into the environment due to their toxicity and, in particular, due to the long half-lives of some of their isotopes and those of their daughter elements. Because of these concerns the importance of separating individual actinide elements from one another or from the other elements in the nuclear fuel cycle, as well as furthering the understanding of the environmental chemistry of the relevant actinide and actinyl complexes, has been and is now even more so, the focus of many ongoing and growing numbers of research efforts [2, 3]. Under the general theme of ―actinyl containing complexes‖ we investigate, through the use of computational methods, two unique categories of molecular structures. Through such efforts we are looking to build on the existing level of knowledge of these 1
Page 1 and 2: A Density Functional Study of Actin
Page 3 and 4: Acknowledgements I would like to th
Page 5 and 6: 2.1.3 Kohn-Sham Molecular Orbitals
Page 7 and 8: 4.3.1.1 Metal Coordination ........
Page 9 and 10: List of Tables Table 3-1. Calculate
Page 11 and 12: List of Figures Figure 1-1. Radial
Page 13 and 14: List of Copyrighted Material for wh
Page 15: Eq. or Eqn. equation etc. et cetera
Page 19 and 20: eactivity of the early actinides wi
Page 21 and 22: appendix, for supplementary materia
Page 23 and 24: the exception of depleted uranium s
Page 25 and 26: all the actinides being radioactive
Page 27 and 28: early actinides the addition of eac
Page 29 and 30: generally considered to be a partia
Page 31 and 32: 1.3.3 Early Actinides and Actinyls
Page 33 and 34: �� CHAPTER TWO GENERAL T
Page 35 and 36: �� f i �� HF ��
Page 37 and 38: investigations into intermediate si
Page 39 and 40: �� 2.1.2 Exchange-Correlation F
Page 41 and 42: �� In ADF Slater type orbitals
Page 43 and 44: �� nucleus by the stabilized ou
Page 45 and 46: �� 2.2.1 The Scalar Four
Page 47 and 48: H � � T �VRECP Vval (2-16) Fo
Page 49 and 50: y a dielectric constant (ε). The d
Page 51 and 52: orders [64, 65] and Hirshfeld atomi
Page 53 and 54: The Hirshfeld charge on an atom A i
Page 55 and 56: Pasilis et al. [73] recently used e
Page 57 and 58: oader goal we look to show that a c
Page 59 and 60: as the core and the remaining elect
Page 61 and 62: 3.3 Results and Discussion The proc
Page 63 and 64: Several other gas-phase isomers of
Page 65 and 66: Figure 3-1. Structural components:
Page 67 and 68:
structural parameters (g03 B3LYP/cc
Page 69 and 70:
ands of 19 are 1290 cm -1 for the s
Page 71 and 72:
types were identified. The third ca
Page 73 and 74:
Figure 3-4. Optimized UN4O12 isomer
Page 75 and 76:
Figure 3-5. Optimized UN4O12 isomer
Page 77 and 78:
subject to different interpretation
Page 79 and 80:
covalent/ionic character rather tha
Page 81 and 82:
Figure 3-6. ∆μ (♦, Debye) vers
Page 83 and 84:
3.3.3.4 Bond Lengths, Angles, Bond
Page 85 and 86:
Table 3-4. Calculated bond lengths
Page 87 and 88:
Table 3-6. Calculated Hirschfeld at
Page 89 and 90:
Table 3-7. Calculated vibrational f
Page 91 and 92:
epresented. The proceeding discussi
Page 93 and 94:
3.3.4.2 a-series type 6: a4, a5, a1
Page 95 and 96:
As for the vibrational frequencies,
Page 97 and 98:
shortest Ny=O bond lengths. The one
Page 99 and 100:
Free energies were calculated, for
Page 101 and 102:
After narrowing down our relative G
Page 103 and 104:
For this study, the use of optimize
Page 105 and 106:
These experimental efforts [125, 12
Page 107 and 108:
through observations of period tren
Page 109 and 110:
obtain thermochemistry data, such a
Page 111 and 112:
complementary ferrocenium/ferrocene
Page 113 and 114:
Figure 4-3. Optimized Case 3 comple
Page 115 and 116:
4.3.1.2 Bond Angles, Bond Lengths,
Page 117 and 118:
1.807 to 1.842 Å, representing rel
Page 119 and 120:
Table 4-4. Gas-phase bond lengths f
Page 121 and 122:
As for the Hirshfeld atomic charges
Page 123 and 124:
oxidation states show a noticeable
Page 125 and 126:
62.0º for An VI and An V complexes
Page 127 and 128:
U VI O23, and 0.52 for Np VI O23 ar
Page 129 and 130:
Furthermore with available experime
Page 131 and 132:
somewhat ad hoc values predicted fo
Page 133 and 134:
addition, computational evidence of
Page 135 and 136:
Actinide separations of spent fuels
Page 137 and 138:
PUREX process for the separation of
Page 139 and 140:
DFT wave function should improve th
Page 141 and 142:
Experimental bond lengths for dioxy
Page 143 and 144:
chemically and are rapidly hydrolyz
Page 145 and 146:
A.1.1.6 Dinitrogen Pentoxide In the
Page 147 and 148:
labeled as TS21. The perpendicular
Page 149 and 150:
type 11 containing cis,trans-ON·OO
Page 151 and 152:
Both an NO + and an NO2 ligand can
Page 153 and 154:
Figure A-6. Optimized UN4O12 isomer
Page 155 and 156:
BIBLIOGRAPHY 1. Berard, J.J., Shamo
Page 157 and 158:
38. Lee, C., Yang, W., and Parr, R.
Page 159 and 160:
79. Brouard, M., et al., J. Chem. P
Page 161:
122. Veauthier, J.M., et al., Inorg
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