Electronic Structure Across the Periodic Table: Chemistry of the Large in Mass and the Small in Size Dissertation Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Michael Kiyoshi Mrozik, B.A. Graduate Program in Chemistry The Ohio State University 2011 Dissertation Committee: Dr. Christopher M. Hadad, Adviser Dr. Russell M. Pitzer Dr. Claudia Turro Dr. Bruce E. Bursten Dr. Chenglong Li Copyright by Michael Kiyoshi Mrozik 2011 Abstract The results of several investigations are presented in this work. Each project results from research using applied theoretical simulations and electronic structure programs to elucidate and understand several difficult and complex problems from the bottom to the top of the periodic table. Work within each of these projects contain efforts to understand ground, low-lying (≤ 2eV) or highly excited (≥ 500eV) electronic states. 2+ Reactions involving the thorium analog to ferrocene ([Cp2Th] ) were studied, using relativistic effective core potentials and density functional theory, to explore ∗ IV the accessibility of linear thorocene from Cp2Th Ln complexes. Newly predicted IV ground-state structures of the form Cp2Th Ln where n = 1-5 are reported, where L − − − − − − − − − = [F] , [Cl] , [Br] , [I] , H2O, [NH2] , [NCS] , NCMe, [CN] , [CHCH2] , [CH3] , CO and pyridine N-oxide. With the exception of the amido complexes, all ground states contain a linear Cp2Th unit. The requirements for forming linear actinocene moieties are discussed in light of current results and existing experimental efforts with uranium metallocene complexes. The activation of small (C1-C4) alkanes and alkenes by bare and oxo-ligated ac- tinide cations (Th+ through Cm+) has been systematically examined using Fourier transform ion cyclotron resonance mass spectrometry. The reactivity trend identified for the highly reactive early actinide ions, Th+ > Pa+ > U+ > Np+, is interpreted to ii indicate significant 5f electron participation in organoactinide σ-type bond formation for Pa+. Among the seven studied AnO+ ions, only ThO+, PaO+, and UO+ activated at least one hydrocarbon, with the reactivity of PaO+ being distinctively high. Elec- tronic structure calculations for PaO+ show that its ground state is [Pa(5f6d)O]+, i.e., with one 5f and one 6d nonbonding electrons available on the metal, and all of its excited states up to 1.8 eV have a 5f orbital occupancy of ≥0.8. The high re- activity and substantial 5f character of PaO+ indicate participation of 5f electrons in hydrocarbon bond activation for oxo-ligated Pa+. The results of this work reveal that 5f electrons play a distinctive role in protactinium chemistry involving σ-type organometallic bonding. The lower energy levels of the protactinium (Pa) atom are unusually difficult to treat theoretically. Pa is located where the 6d and 5f energies cross; simple calculations consistently put the electron configurations 5f 16d27s2 and 5f 26d17s2 in the incorrect order. We have used multireference spin-orbit configuration interaction to compute the energies of these states to determine which additional interactions need to be included. We also discuss the less common J1j coupling scheme suggested for these atomic states with applications also to the 5f 16d2 and 5f 26d1 states of Pa2+. The core-excitation of electrons and formation of valence resonance states were determined for the water monomer and attempted for dimer. Excitation energy for removal of an electron from the oxygen 1s type atomic orbital to the available anti- bonding valence orbitals is modeled using spin-orbit configuration interaction with single and double excitations. Initial determinations of excitation energy, oscillator iii strengths and transition dipole magnitudes were obtained. The oscillator strengths for transitions in the dimer appear to show a dependence on the molecular orbital density localization. iv Dedicated to My Parents, Family, and Sam v Acknowledgments The undertaking of graduate school and the doctoral thesis that occasionally re- sults from such endeavors, is not an journey to be undertaken for everyone. The rigors of the classwork, demands of the research, difficulties with teaching, and not to mention the pressures of striking out as an adult with the weight of the world on your shoulders is just some of what goes on. In order to survive this trip physically and emotionally there need to be people helping and often too many ways to iden- tify, but it is my opportunity here to attempt to put in a more permanent record an acknowledgement of some of the people who have gotten me to this point. I would like to thank all of them personally, but that may not be possible. So I have com- piled a list of those who deserve my sincerest thanks, and I look to make sure that their importance is not forgotten, by me or anyone who might pick up this document sometime down the road... Dr. R. M. Pitzer (Dr. P.): I don’t think I can tell you how much I feel I owe to you and all that you have done for me over the years. Part of your role has been as my advisor and for that I have to thank you so very much. Not just for taking me as your student when you did not vi have to, but for looking out for me in so many ways. You have seen me at both my highest and lowest moments over the past few years, and I find it hard to think of what would happen if your steady guidance and oversight had not been there for me. I only hope that I can live up to and provide the same type of caring mentorship to my own students down the road. I will forever tell some of the stories that you have so graciously shared with me over the years, but even with years of practice, I may get close, but will never be able to duplicate your comedic timing. Dr. A. B. McCoy: As a surrogate advisor, adopting me as part of the McCoy research family has meant a lot. From your efforts to reassure a freaked out first year student to the encourage- ment of a tired senior grad student, the impact of your presence has been a constant force pushing me to achieve and deserves to be acknowledged. The cumulative time spent advising and providing guidance over the years has not gone unnoticed, and I find it hard to express the extent of my gratitude for everything. So simply thank you for all that you have done for me; I am grateful to consider you not only as one of my advisors with the completion of my dissertation, a colleague, but more importantly a friend. Dr. Samantha Horvath: Like the other individuals to be acknowledged here, I think it is hard to detail or document your importance in getting me to this point. In significance I find it nearly vii impossible to quantify how much you have meant to me or how I much value your support and friendship since starting my time in Columbus. From the study ses- sions for our courses over at friends’ apartments our first year to the proof reading of my presentations and posters for conferences, in an academic setting there is little I think that you did not influence. And while I may have helped teach you a little linear algebra and maybe a little bit of group theory, I think we both know it was partly out of a desire to spend more time together. Some six years later and you still pass along encouragement and continue to remind me of what you termed to as “my awesomeness”. It is for these reasons, for all the other things you do for me, and for all that you mean to me that I wanted to thank you. From “Hero” to butter cows; nervous sushi dining to Disney; the greatest candle shop in the world to “Wild Lights” at the Zoo; we have been on so many adventures together. I simply can not wait for the journeys that we are yet to embark on and look forward to wherever the future explorations may take us, and most of all I look forward to doing them together. My Parents: I do not know how or if I can put into words all that you and your eternal support have meant to me. I think if I said that graduate school and college have been a challenging period for the us as a family, and me as an individual, it would be an understatement of mammoth proportion. But through all of the difficulties and chal- lenges you were a constant, helping to guide me through the maze leading me to today. I guess with the completion of this document, it would be a validation for all viii your efforts as parents, from reading me “Pickle Things” and “Momotaro” as a child to proof-reading my college application essay. I know I did not make things easy on you, by perpetually attempting to solve my own problems and not sharing many of the private aspects of my life, but through it all you guys were there to cheer me on. That steadfast support has always meant so much to me, from freezing baseball games reminding me to “Rock and Fire!”, raining soccer games and joking about the number of opposing “dead” players I was generating, uncomfortable bleachers at volleyball matches, to even putting up with my golf “obsession” and taking me to the golf convention at Navy Pier. All the little things over the years, like lessons on how to make the perfect Japanese rice and making stir-fry (Sam greatly appreciates the last one) to all the conversations about movies, politics, books or whatever happened to be sticking in my brain.