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Table of Contents Abstract....................................................................................................................................ii Acknowledgements............................................................................................................... iii Table of Contents .................................................................................................................. iv List of Tables .......................................................................................................................... ix List of Figures ........................................................................................................................ xi List of Copyrighted Material for which Permission was Obtained ........................... xiii List of Abbreviations ..........................................................................................................xiv CHAPTER ONE INTRODUCTION .................................................................................................................. 1 1.1 Motivation .................................................................................................. 1 1.2 Overview .................................................................................................... 2 1.3 The Early Actinides and their Actinyls ................................................. 5 1.3.1 Electronic Configurations of Early Actinides ................................. 9 1.3.2 Electronic Strucure of Actinyls ....................................................... 12 1.3.3 Early Actinides and Actinyls in Aqueous Solution ...................... 15 1.3.4 Early Actinides and Actinyls in Nonaqueous Solutions .............. 15 CHAPTER TWO GENERAL THEORY AND APPROXIMATION METHODS ................................... 17 2.1 Density Functional Theory .................................................................... 20 2.1.1 Nonrelativistic Total Energy ............................................................ 21 2.1.2 Exchange–Correlation Functionals ................................................ 23 iv
2.1.3 Kohn–Sham Molecular Orbitals and Basis Set Expansion......... 23 2.1.3.1 Auxiliary Basis Set Expansion .................................................... 25 2.2 Relativistic Effects .................................................................................. 26 2.2.1 The Scalar Four–Component Method ........................................... 29 2.2.2 The Zero Order Regular Approximation (ZORA) Method ....... 29 2.2.3 Relativistic Effective Core Potentials (RECPs)............................. 30 2.2.4 Spin–Orbit Coupling ......................................................................... 31 2.3 Solvation Methods .................................................................................. 32 2.3.1 COSMO and C–PCM ....................................................................... 32 2.4 Molecular Properties Investigated ....................................................... 34 2.4.2 Hirshfeld Atomic Charges ................................................................ 36 CHAPTER THREE DENSITY FUNCTIONAL STUDY OF THE VARIOUS FORMS OF UN4O12 CONTAINING URANYL NITRATE ............................................................................... 38 3.1 Introduction ............................................................................................. 38 3.2 Computational Methods ........................................................................ 41 3.3 Results and Discussion ........................................................................... 45 3.3.1 The Structural Components ............................................................ 47 3.3.2 Classifications of UN4O12 Isomers Containing Uranyl Nitrate .. 54 3.3.2.1 N2O4 Adducts................................................................................. 55 3.3.2.2 Nitrosonium Salts ......................................................................... 58 3.3.2.3 2·NO2 Adducts ............................................................................... 59 3.3.3 General Analysis and Discussion of Selected UN4O12 Isomers ... 60 v
Page 1 and 2: A Density Functional Study of Actin
Page 3: Acknowledgements I would like to th
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 and 16: Eq. or Eqn. equation etc. et cetera
Page 17 and 18: 1.1 Motivation CHAPTER ONE INTRODUC
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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