RELIABLE PREDICTIONS OF THE PROPERTIES OF ACTINIDE COMPLEXES by VIRGIL ...

242 Pages·2013·4.95 MB·English

by  V. E. Jackson

RELIABLE PREDICTIONS OF THE PROPERTIES OF ACTINIDE COMPLEXES

by

VIRGIL EDWARD JACKSON
DAVID A. DIXON, COMMITTEE CHAIR
SHANE C. STREET
GREGORY SZULCZEWSKI
LOWELL D. KISPERT
TONYA M. KLEIN

A DISSERTATION

Submitted in partial fulfillment of the requirements
for the degree of Doctor of Philosophy
in the Department of Chemistry
in the Graduate School of
The University of Alabama

TUSCALOOSA, ALABAMA

2013
Copyright Virgil Edward Jackson 2013
ALL RIGHTS RESERVED
ABSTRACT
A study of reactions of laser-ablated thorium atoms and O using matrix
2
isolation infrared spectroscopy has been conducted using electronic structure
calculations to interpret the infrared spectra of three new thorium oxide species,
ThO -, Th O , and Th O obtained in argon and neon matrixes.
2 2 2 2 4
The potential energy surface for the reaction of matrix isolated ThO with CH to give the
4
CH Th(O)H intermediate has been calculated at the CCSD(T) level, it reveals that the
3
CH Th(O)H molecule possesses a pyramidal structure with a closed shell singlet ground state.
3
Formation of the CH Th-(O)H molecule from the reaction of ThO and methane has an energy
3
barrier of 30 kcal/mol, which is consistent with the appearance of the 1CH Th(O)H absorptions
3
under broad band mercury arc UV irradiation. The 3Th + 1CH OH asymptote is predicted to be
3
119 kcal/mol above the reactant asymptote, 1ThO + CH ,utilizing the spin orbit correction to the
4
3Th atom which is in excellent agreement with the value of 118.7 ± 3.8 kcal/mol.
The first reliable predictions of the frequencies of the isolated uranyl ion have been made
to develop new techniques to determine how this important form of uranium is being complexed
in the environment. A comprehensive computational study of UO 2+ complexed with the
2
phosphate anions H PO -, HPO 2-, and PO 3- and water ligands has been performed at the density
2 4 4 4
functional theory (DFT) and correlated molecular orbital theory levels in the gas phase and in
aqueous solution. This study was done to aid the effort in developing solutions to the in situ
remediation challenge posed by the nuclear waste stored in the tanks at the Hanford and
ii
Savannah River nuclear weapons production sites. This information can be used to provide a
better understanding of the speciation of such species and to better our understanding of mobility
issues of tank waste as well as stability concerns for waste matrices.

iii
DEDICATION
To my mom, Virginia Jackson, and my dad, Edward Jackson, for their love and support; without
which my success would not have been possible.
iv
LIST OF ABBREVIATIONS AND SYMBOLS

ADE Adiabatic electron affinity
ADF Amsterdam Density Functional software
aug-cc-pVnZ Augmented, correlation consistent, polarized valence n zeta basis sets,
where n = double (D), triple (T) or quadruple (Q)

ANO-L Large atomic natural orbital basis sets
ANO-S Small atomic natural orbital basis sets
aug-cc-pVnZ-PP aug-cc-pVnZ basis sets with pseudopotentials for heavy atoms
aug-cc-pwCVnZ Augmented, correlation consistent, polarized weighted core valence n
(D, T, Q or 5) zeta basis sets

aug-cc-pwCVTZ-PP aug-cc-pwCVTZ basis set with pseudopotentials for heavy atoms
AVDZ E(n) = E + A exp[−(n − 1)] + B exp[−(n − 1)2]
CBS
n = 2 (aug-cc-pVDZ-PP)

AVTZ E(n) = E + A exp[−(n − 1)] + B exp[−(n − 1)2]
CBS
n = 3 (aug-cc-pVDZ-PP)

AVQZ E(n) = E + A exp[−(n − 1)] + B exp[−(n − 1)2]
CBS
n = 4 (aug-cc-pVDZ-PP)

awCVTZ aug-cc-pwCVTZ basis sets
B3LYP Becke 93 (exchange), Lee-Yang-Parr (correlation) DFT functional
BLYP Becke 88 (exchange), Lee-Yang-Parr (correlation) DFT functional
BDE Bond dissociation energy
BP86 Becke 88 (exchange), Perdew 86 (correlation) DFT functional
v
CAS Complete active space
CASPT2 Complete active space second-order perturbation theory
CBS Complete basis set
CCSD(T) Coupled cluster singles, doubles, and disconnected triples
CCSD Coupled cluster singles, doubles
COSMO Conductor-like screening model
CI Configuration interaction
CISD Configuration interaction singles and doubles
CV Core valence
DFT Density functional theory
DHF Dirac–Hartree–Fock
DZVP DFT optimized double zeta valence basis set with polarization functions
(except H)

DZVP2 DFT optimized double zeta valence basis set with polarization functions
ΣD (ΣD ) Total atomization energy
0 0,0K
G3MP2 Gaussian 3 theory calculation using 2nd order Møller Plesset
perturbation theory (MP2)

ΔE Complete basis set energy change
CBS
ΔE Core valence energy change
CV
ΔE Pseudopotential error correction energy exchange: ΔE = ΔE
PP,corr PP,corr awCVTZ-
- (ΔE + ΔE ).
DK awCVTZ-PP SR

ΔE Scalar relativistic energy change: ΔE = ΔE + ΔE = ΔE
Rel Rel SR PP,corr awCVTZ-
- ΔE
DK awCVTZ-PP

ΔE Spin orbit energy change
SO
ΔE Scalar relativistic correction calculated as the MVD expectation values
SR
vi
ΔE Zero point energy change
ZPE
ΔE /ΔE BDE at 0 K/298 K
0K 298K
ECP Effective core potential
EA Electron affinity
FA Fluoride affinity
FCF Franck-Condon factors
(FT-ICR-MS) Fourier transform ioncyclotron resonance mass spectrometry
FTIR Fourier transform infrared spectroscopy
FWAM Full widths at half maximum
ΔG Aqueous deprotonation Gibbs free energy (solution free energy)
aq
ΔG Gas phase free energy
gas
ΔΔG Aqueous solvation free energy
solv
ΔG Gas phase Gibbs acidity
298K
GIAO Gauge independent atomic orbital approximation
ΔH Gas phase enthalpy acidity
298K
HA Hydride affinity
HF Hartee-Fock
ΔH Heat of formation at 0K
f,0K
ΔH Heat of formation at 298K
f,298K
ΔH Reaction enthalpy change
rxn
I Intensities
IR Infrared spectrscopy
K Kelvin
vii
MO Molecular orbital
MP2 2nd order Møller Plesset perturbation theory
MVD Mass-velocity and Darwin operators
NIST-JANAF National Institute of Standards and Technology - Joint Army-Navy-Air
Force

NMR Nuclear magnetic resonance
PA Proton affinity
PBE Perdew-Burke-Ernzerhof (exchange), Perdew-Burke-Ernzerhof
(correlation) DFT functional

PES Potential energy surface
pK Negative logarithm of the acid dissociation constant
a
PP Pseudopetential
PW91 Perdew-Wang 91 (exchange), Perdew-Wang 91 (correlation) DFT
functional

R Restricted method for the starting Hartree–Fock wavefunction
R Gas constant
ROHF Open-shell HF
R/UCCSD(T) Open-shell CCSD(T)
SCF Self consistent field
SCRF Self consistent reaction field
SO Spin orbit
SP Square pyramidal
SR Scalar relativistic
T Temperature
viii
TAE Total atomization energy
TZ2P Triple zeta basis set with 2 polarization functions
UV Ultraviolet
VTZP Valence high triple zeta basis set with polarized function
ZORA Zeroth order regular approximation to the Dirac equation
ZPE Zero point energy
> Greater than
< Less than
= Equal to
Å Angstrom
° Degrees
± Plus or minus

ix