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Quantum Chemistry Calculations of Energetic and Spectroscopic QUANTUM CHEMISTRY CALCULATIONS OF ENERGETIC AND SPECTROSCOPIC PROPERTIES OF p- AND f-BLOCK MOLECULES Christopher South, B.S. Dissertation Prepared for the Degree of DOCTOR OF PHILOSOPHY UNIVERSITY OF NORTH TEXAS August 2016 APPROVED: Angela K. Wilson, Major Professor Thomas R. Cundari, Committee Member Paul Marshall, Committee Member Simone Raugei, Committee Member Michael Richmond, Committee Member and Chair of the Department of Chemistry David Holdeman, Dean of the College of Arts and Sciences Victor Prybutok, Vice Provost of the Toulouse Graduate School South, Christopher. Quantum Chemistry Calculations of Energetic and Spectroscopic Properties of p- and f-Block Molecules. Doctor of Philosophy (Physical Chemistry), August 2016, 19 tables, 19 figures, 390 numbered references. Quantum chemical methods have been used to model a variety of p- and f-block chemical species to gain insight about their energetic and spectroscopic properties. As well, the studies have provided understanding about the utility of the quantum mechanical approaches employed for the third-row and lanthanide species. The multireference ab initio correlation consistent Composite Approach (MR-ccCA) was utilized to predict dissociation energies for main group third-row molecular species, achieving energies within 1 kcal mol-1 on average from those of experiment and providing the first demonstration of the utility of MR-ccCA for third-row species. Multireference perturbation theory was utilized to calculate the electronic states and 2+ dissociation energies of NdF , providing a good model of the Nd-F bond in NdF3 from an electronic standpoint. In further work, the states and energies of NdF+ were determined using an equation of motion coupled cluster approach and the similarities for both NdF2+ and NdF were noted. Finally, time-dependent density functional theory and the static exchange approximation for Hartree-Fock in conjunction with a fully relativistic framework were used to calculate the L3 2+ ionization energies and electronic excitation spectra as a means of characterizing uranyl (UO2 ) + and the isoelectronic compounds NUO and UN2. Copyright 2016 By Christopher South ii ACKNOWLEDGEMENTS Obtaining a PhD. is never done on your own efforts alone. I thank the individuals who have helped me these past five years. First, I would like to thank my advisor, Dr. Angela Wilson for all the help and support she has given me. I would also like to thank Drs. Thomas Cundari, Simone Raugei, Neeraj Kumar, Trond Saue and Avijit Shee for their valuable advice and insight for the collaborative research projects. The following postdocs were invaluable to me during my time at the University of North Texas: Drs. Wanyi Jiang, George Schoendorff, and Deborah Penchoff. I would like to thank the other members of the Wilson group: Dr. Becky Weber, Dr. Jiaqi Wang, Dr. Andrew Mahler, Dr. Amanda Riojas-Brown, Chris Jeffrey, Matthew Carlson, Prajay Patel, Cesar Plascencia, Zainab Alsunaidi, John Pearson, and Michael Jones for their support and feedback during my time in the group. I would like to thank my parents Dr. Bob South and Kathy South for their support and encouragement during my graduate career. Without their support and reminders, I would not have made it nearly as far as I have. I would also like to thank my brothers Matt and Steve for their support and companionship as well. Finally, I would like to thank my Lord and Savior Jesus Christ for giving me the strength to persevere through these five years ever present deadlines and intercontinental travel so I could get to this point. Lastly, I would especially like to thank the following organizations for providing support, computational resources, and travel opportunities for my work: the National Science Foundation, the Department of Energy, the American Chemical Society, the Toulouse Graduate School at the University of North Texas, and the Department of Chemistry at the University of North Texas. iii TABLE OF CONTENTS Page ACKNOWLEDGEMENTS ........................................................................................................... iii LIST OF TABLES ........................................................................................................................ vii LIST OF FIGURES ....................................................................................................................... ix CHAPTER 1 INTRODUCTION .............................................................................................1 CHAPTER 2 COMPUTATIONAL THEORY ........................................................................5 Section 2.1 Schrödinger’s Equation ................................................................................5 Section 2.2 Basis Sets .....................................................................................................6 Section 2.3 Hartree-Fock ..............................................................................................10 Section 2.4 Single Reference Correlation Methods ......................................................12 Section 2.5 Multi-reference Methods and Other Static Correlation Methods ..............16 Section 2.6 Density Functional Theory ........................................................................19 Section 2.7 Excited State Methods ...............................................................................20 Section 2.8 Relativistic Methods ..................................................................................21 Section 2.9 Composite Methods ...................................................................................24 CHAPTER 3 MR-ccCA: A ROUTE FOR ACCURATE GROUND AND EXCITED STATE POTENTIAL ENERGY CURVES AND SPECTROSCOPIC PROPERTIES FOR THIRD-ROW DIATOMIC MOLECULES ...................27 Section 3.1 Introduction ................................................................................................27 Section 3.2 Methodology ..............................................................................................32 Subsection 3.2.1 MR-ccCA Composition ........................................................32 Subsection 3.2.2 Research Specifics ................................................................36 iv Section 3.3 Results and Discussion ..............................................................................37 Subsection 3.3.1 Ground State Potential Energy Curves .................................37 Subsection 3.3.2 As2 Excited States .................................................................45 Section 3.4 Conclusion .................................................................................................47 CHAPTER 4 A NEOTERIC NEODYMIUM MODEL: GROUND AND EXCITED ELECTRONIC STATE ANALYSIS OF NdF2+ .............................................61 Section 4.1 Introduction ................................................................................................61 Section 4.2 Computational Details ...............................................................................63 Section 4.3 Results ........................................................................................................66 Section 4.4 Conclusions ................................................................................................73 CHAPTER 5 DISSOCIATION ENERGY AND ELECTRONIC STRUCUTRE OF THE LOW VALENT LANTHANIDE COMPOUND NdF+ ...................................80 Section 5.1 Introduction ................................................................................................80 Section 5.2 Methodology ..............................................................................................82 Section 5.3 Results and Discussion ..............................................................................83 Section 5.4 Conclusion .................................................................................................88 CHAPTER 6 4-COMPONENT RELATIVISTIC CALCULATIONS OF L3 IONIZATION 2+ + AND EXCITATIONS FOR THE ISOELECTRONIC SPECIES UO2 , OUN AND UN2 .........................................................................................................90 Section 6.1 Introduction ................................................................................................90 Section 6.2 Theory ........................................................................................................93 Subsection 6.2.1 Core Ionization......................................................................93 Subsection 6.2.2 Core Excitation .....................................................................96 v Subsection 6.2.3 Projection Analysis .............................................................101 Section 6.3 Computational Details .............................................................................102 Section 6.4 Results and Discussions ...........................................................................104 Subsection 6.4.1 Molecular and Electronic Structures ...................................104 Subsection 6.4.2 Uranium 2p Binding Energy ...............................................107 Subsection 6.4.3 Uranium L3 Edge XANES Spectra .....................................111 Section 6.5 Conclusions and Perspectives ..................................................................122 CHAPTER 7 CONCLUSIONS............................................................................................123 APPENDIX A A NEOTERIC NEODYMIUM MODEL: GROUND AND EXCITED ELECTRONIC STATE ANALYSIS OF NdF2+ SUPPLEMENTARY
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