A relativistic density functional study of uranyl hydrolysis and complexation by carboxylic acids in aqueous solution [Elektronische Ressource] / Rupashree Shyama Ray

Description

Department Chemie Fachgebiet Theoretische Chemie Technische Universität München A Relativistic Density Functional Study of Uranyl Hydrolysis and Complexation by Carboxylic Acids in Aqueous Solution Rupashree Shyama Ray Vollständiger Abdruck der von der Fakultät für Chemie der Technischen Universität München zur Erlangung des akademischen Grades eines Doktors der Naturwissenschaften (Dr. rer. nat.) genehmigten Dissertation. Vorsitzender: Univ.-Prof. Dr. K.-O. Hinrichsen Prüfer der Dissertation: 1. Univ.-Prof. Dr. N. Rösch 2. Univ.-Prof. Dr. A. Türler Die Dissertation wurde am 15.01.2009 bei der Technischen Universität München eingereicht und durch die Fakultät für Chemie am 10.02.2009 angenommen. 2Acknowledgement It was a grand opportunity and great exposure for me to do a Ph.D. at TU München. During my Ph.D. I have worked w ith a great number of people whose contribution in assorted ways to the research and the making of the thesis deserve special mentioning. It is a pleasure to convey my gratitude to them all in my humble acknowledgment. First of all, I would very much like to thank Prof. Dr. Notker Rösch for his supervision, guidance and advice throughout my Ph.D. career as well as for giving me an extraordinary exposure to the frontiers of science.

Informations

• Publié par: technische_universitat_munchen
• Publié le: 01 janvier 2009
• Nombre de lectures: 76
• Langue: English
• Poids de l'ouvrage: 11 Mo

Extrait

ie mnt CheeDepartm

ieFachgebiet Theoretische Chem

Technische Universität München

A Relativistic Density Functional Study of

rUranyl Hydtion by Carboxylic Acids ysis and Complexaol

in Aqueous Solution

Rupashree Shyama Ray

ie der Technischen Universität für ChemVollständiger Abdruck der von der Fakultät

ischen Grades eines München zur Erlangung des akadem

t.) issenschaften (Dr. rer. naDoktors der Naturw

genehmigten Dissertation.

Vorsitzender:

Prüfer der Dissertation:

1.

2.

Univ.-Prof. Dr. K.-O. Hinrichsen

Univ.-Prof. Dr. N. Rösch

Univ.-Prof. Dr. A. Türler

ersität München r Technischen Univ 15.01.2009 bei deDie Dissertation wurde am

n. eie am 10.02.2009 angenommfür Chemeingereicht und durch die Fakultät

2

ledgement Acknow to do a Ph.D. at TU München. ee for mIt was a grand opportunity and great exposurDuring my Ph.D. I have worked w ith a great number of people whose contribution in
assorted ways to the research and the making of the thesis deserve special mentioning. It is
a pleasure to convey my gratitude to them all in my humble acknowledgment.

nk Prof. Dr. Notker Rösch for his supervision, ch like to thauFirst of all, I would very mr giving me an extraordinary o Ph.D. career as well as fyguidance and advice throughout mtuition and insight has aordinary scientific inexposure to the frontiers of science. His extrmade him a constant oasis of ideas and passions in science, which was a great source of
inspiration for me. Above all his spirit and dedication always provided me unflinching
ent in various ways. encouragem

for his advice, supervision and crucial Krüger nI gratefully acknowledge Dr. Sveis research and thus to this thesis. His a backbone of thde himacontribution, which minvolvement with his originality has triggered and nourished my intellectual maturation,
which will benefit me for a long time to come. I am greatly indebted to Sven for his
c issues. iic and nonacademextended help and support in academ

nt to Prof. T.eI convey special acknowledgem P. Radhakrishnan and Prof. K. D. Sen fortheir indispensable endorsement throughout my scientific career.

mbers Dr. F. eesent minide group past and prIt is a pleasure to pay tribute to the actSchlosser, Dr. L. Moskaleva, A. Kremleva, S. N. Derrar, and Dr. O. Zakharieva for
stimulating discussions as well as for the pleasant work culture in the team. Collective and
individual acknowledgements are also owed to my colleagues: Dr. A. Matveev, Dr. A.
Genest, G. Dixit, G. Galstyan, R. Ramakrishnan, H. Alexandrov, D. Başaran, Dr. B.
irov, M. Metzner, M. H. Rotllant, G. Petrova, and adimell, S. Parker, Z. Zhao, E. VlrMartothose not mentioned here, whose presence was refreshing, helpful, and memorable. Very
many thanks to the secretary Frau Mösch for her friendly gesture and help in
nistrational issues. iadm

My parents deserve special mention for their inseparable love, care and blessings. Without
rds fail to express my o today. Wat I amtheir consistent support I would not be whappreciation to my sister Baijayanti, brother Manmath and sister-in-law Chinmayee whose
love, support and persistent confidence in me made my way much easier through ups and
downs.

esisthis th .

portant to the successful realization of ims

Finally, I would like to thank everybody who wa

drajit,

Vijay, Kali, In

eheartedly to Jayanta,

y gratitude whol

It is a pleasure to express m

. ehom

ble friendship and support. My special

Sushree and Snigdha for their indispensa

m for their

d Siha

l, Raghu, Divita an

ent to Kiran, Somnath, Gopaacknowledgem

cooperation and providing m

e an amiable atmosphere in a foreign land, m

iles away fro m

e, illumination. The means or instrument Knowledge has three degrees -- opinion, scienc

third, intuition.ond, dialectic; of the of the first is sense; of the sec

tinus---Plo

Dedicated to my family

Contents Introduction 1 1 odeling utational mpActinide compounds and their com1.1 overview and 1.2 Motivation 7 Actinide chemistry introduction2 istry General actinide chem2.1 2.1.1 Uranium lexation and stability constant pCom2.1.2 2.1.3 Hydrolysis istry ental chemActinide environm2.2 c substances iActinide interaction with hum2.2.1 complexes 2.2.2 Ternary ntal identification and characterization eExperim2.3 25 method3 Computational thods eDensity functional m3.1 thodseEvaluation of exchange-correlation m3.1.1 thod e functional mdensity3.1.2 Relativistic solvation effects Modeling of3.2 istry mSolvent effects in quantum che3.2.1 odel (COSMO)The conductor like screening m3.2.2 sets 3.3 Basis ization optim3.4 Structure

i

1 4

7 9 9 12 15 18 21 23

25 26 28 29 29 30 32 33

ii

frequencies 3.4 Vibrational 3.5 Thermodynamic corrections
Results and discussion 4nohydroxide om4.1 Uranyl 4.1.1 Models etry 4.1.2 Geom4.1.3 Energetics Free energy of hydrolysis 4.1.4 4.1.5 Conclusion Uranyl complexation by carboxylate ligands 4.2 lexes pcom4.2.1 Monoacetate atic carboxylic acids lexes of arompCom4.2.2 atic carboxylic acids Acidity of arom4.2.2.1 odels m4.2.2.2 Csodels m4.2.2.3 C1constants 4.2.2.4 Stability 4.2.2.5 Implications for uranyl complexation by humic acids
4.2.2.6 Conclusion anyl-hydroxo-acetate 93 Ternary complexes: ur4.3 4.3.1 Models etry 4.3.2 Geom 4.3.3 Energetics Stability constants 4.3.4 4.3.5 Comparison to experiment
4.3.6 Conclusion ary and outlook Summ5 Appendix  Basis Sets Bibliography 117

33 35

37 38 39 39 51 53 55 57 57 62 63 65 77 87 91 92 94 95 100 103 105 107 109

113

iii List of Abbreviations units ic au atomnge-correlation functional) Becke-Perdew (exchaBP lated calcuCalc.second-order perturbation theory lete active space with pcomCASPT2 urbative Triple and Double and pertCoupled-cluster with Single CCSD(T)ethod) excitations (method) Configuration Interaction (mCI er bnumCN Coordination odel mscreening COSMO conductor-like functional DF density DFT density functional theory
ethod) (mDHF Dirac-Hartree-Fock (procedure) DK Douglas-Kroll (procedure) DKH Douglas-Kroll-Hess DKS Dirac-Kohn-Sham (method, Hamiltonian)
effective core potential ECP extended x-ray absorption fine structure spectroscopyEXAFS ntal eExp. experimcore FC frozen unction fitting FF fGGA generalized gradient approximation (of xc functional)
ethod) (mHF Hartree-Fock lecular orbital oHighest occupied mHOMO LUMO Lowest unoccupied molecular orbital

iv

KS Kohn-Sha

LCGTO

LDA

LDA/BP

MO

m (method, Hamiltonian)

Gaussian-type orbitals ination ofbr comlinea

tion (of xc functional) alocal density approxim

etry BP single point on LDA geom

l bitarmolecular o

leMøller-PMP2 second-order sset perturbation theory

resonance gnetic amNMR nuclear

PBEN Perdew-Burke-Ernzerhof (exchange-correlation functional), modified

. et al Nørskov ing toaccord

continuumPCM polarizable model

PP Pseudopotential

chanics em QM quantum

RECP relativistic effective core potential

field (procedure) SCF self-consistent

thod) espin-orbit (interaction, mSO

SR scalar-relativistic

-resoTRLFS Timepy fluorescence spectroscolved laser-induced

UAHF

vdW

VWN Vosko-

SXANE

XAS

xc

XRD x-ray

ZORA zeroth-order

ck o  Hartree-Funited atom

aals (radius) van der W

nge-correlation functional) (exchailk-Nusair W

ar edge spectroscopyx-ray absorption ne

x-ray absorption spectroscopy

exchange-correlation (functional, potential, energy)

diffraction

tion (ma approximregularethod)

1 Introduction

Introduction 1 computational modeling Actinide compounds and their 1.1

1

The environment is one of the most intricate systems from a chemists perspective. A very
large number of chemically active compounds and minerals reside within the earths crust.
The interaction of water with rocks and minerals at the atomic level is a poorly understood
phenomenon exhibiting its own chemical processes. Similarly, from a chemists point of
view, the actinides are complex elements, which make the chemical interactions of
actinides in the environment multifarious. Predicting the chemistry and the migration of
conditions. Additionally e analysis of all localent requires thenvironmactinides in the cal processes affecting the actinides ihemquantitative knowledge of the competing geocbehavior is crucial. Precipitation and dissolution of actinides limit the concentration of
actinides in solution, while complexation and redox reactions determine the distribution
and stability of the species. The interaction of a dissolved species with mineral and rock
surfaces and/or colloids determines their migration rates. Understanding this dynamic
interplay between the actinides