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Quantum-Mechanical Evaluation of the Thermodynamics and Kinetics of Environmentally-Relevant Actinide Reactions

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Quantum-Mechanical Evaluation of the Thermodynamics and Kinetics of Environmentally-Relevant Actinide Reactions by Will Martin Bender A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy (Earth and Environmental Sciences) in The University of Michigan 2019 Doctoral Committee: Professor Udo Becker, Chair Associate Professor Rose M. Cory Assistant Professor Brian R. Ellis Professor Mark E. Meyerhoff Will Martin Bender [email protected] ORCID: 0000-0003-1964-9240 © Will Martin Bender 2019 All Rights Reserved DEDICATION For my family, friends, and teachers. ii ACKNOWLEDGEMENTS Many people have played a role in my doctoral degree experience here at Michigan and I will try my best to thank them all here. To those who I may fail to acknowledge, know that I am sorry and that your impact was felt. First off, I would like to thank my advisor, Udo Becker, for the opportunity to work with him at Michigan. Everything that I have accomplished here truly would not have been possible without your guidance, advice, and seemingly limitless source of new ideas. We only spoke briefly before I decided to come and it was a bit of a gut decision, but I really could not be happier with how it turned out. Thank you for giving me the freedom to pursue my interests and helping me find ways to stay positive and apply myself, especially when things didn’t go as planned. In addition to Udo, I would like to thank the other members of my dissertation committee, Brian Ellis, Rose Cory, and Mark Meyerhoff, for their time and feedback throughout my candidacy. I would also like to thank Greg Dick who served as a committee member for several years before we had to make a change due to final scheduling conflicts. I am also very grateful to the research group mates I overlapped with during my degree program: Sarah Walker, YoungJae Kim, Ke Yuan, Ben Gebarski, Sooyeon Kim, Peter Cook, Evan Killeen, Saumitra Saha, and Krishnamoorthy Arumugam. It would not have been the same without you all and you have all helped contribute to the work in this dissertation in some meaningful way. Thank you all for listening to practice presentations and providing constructive feedback, reading iii drafts of proposals and manuscripts, helping with programming quandaries, sharing meals, and providing encouragement at odd hours. I would also like to thank Neal Hughes for his help in the lab during the initial stages of our group’s foray into (photo)electrochemistry. Special thanks to Maria Marcano for all of her tireless efforts in our laboratory space; I don’t know where our group would be without you. I would also like to thank several people who enriched my experience here in the Department and provided me with opportunities outside of my research commitments. Thanks to Jackie Li, Adam Simon, Shelie Miller, and Michela Arnaboldi for letting me serve as a GSI and grader for your courses. My teaching experiences on campus and at Camp Davis were some of the highlights of my time as a graduate student. Thank you also to Gordon Moore and Zhongrui Li who provided the opportunity for me to work in Electron Microbeam Analysis Laboratory. I really learned a lot about the instruments while helping the diverse user-base achieve their analytical goals. Thank you to Marin Clark for allowing me to serve as a graduate student mentor for two years - it was my pleasure and honor. Thank you to the many people who make our department and the graduate student experience function smoothly, particularly Anne Hudon, Nancy Kingsbury, Bill Wilcox, Craig Delap, Dhammika Dewasurendra, Stacey Wilkin, Paula Frank, and Mike Messina. You all helped me in so many ways, whether it was addressing maintenance issues in our lab space, fixing problems with our computing cluster, procuring reagents with student funds, or providing sage advice and reminders about all things degree-related. You are always there for us as graduate students and we would be in such big trouble without you. I have had the pleasure of meeting many great people here during my time at Michigan. I will carry with me lots of fond memories, starting from the days sharing the big first year office iv with Alyssa Abbey, Molly Blakowski, Sam Haugland, Sean Hurt, James Jolles, Evan Killeen, Erin Lynch, Mark Robbins, Collin Ward, and Spencer Washburn. Thanks also to Phoebe Aron, Tristan Childress, Alex Cusick, Joe El Adli, Sharon Grim, Pam Horsley, Tom Hudgins, Lucas Joel, Brian Konecke, Nikita La Cruz, David Levine, Amanda Loh, Ross Maguire, Juliana Mesa, Kyle Meyer, Mackenzie Moore, Jill Myers, Samantha Nemkin, Peng Ni, Xiaofei Pu, Alex Stefanov, Meghan Taylor, Kate Turner, Alex Tye, Meg Veitch, Kalli Washburn, and Ian Winkelstern for all the good times working and playing in our building, around town, and all over the world, from Canada to Chile. Particular thanks to my officemates of the last few years: Alex K., Sharon, Sarah, Sean, and Juliana. Your daily companionship was valued and enjoyed. Thank you also to my friends from childhood and college who I was lucky to have with me in Ann Arbor and the greater Midwest: Hayley Beckett, Sam Kollar, Stacey Rosenzweig, Taro Tomiya, and Julian Watanabe. It was a real treat to reconnect with you all in this new place. I am so glad to have met many friendly and fun people, including many more I failed to list here, and I look forward to more time spent together out in the “real” world. I would like to thank many family members, my parents, Ruth and Dan, my sister, Anna, my Ann Arbor/Dexter/Chelsea-based grandparents, Marilyn and Dale, my Petoskey-based grandmother, Ruth, and my great aunt and uncle, Nancy and Wendel, for all of your love, support, and encouragement. I am especially grateful to my grandparents and extended family who live in Washtenaw County. We spent so many good times together over these years and I learned a lot from you all as you experienced a number of significant life moments – selling a beloved century farm, battling with degenerative disease, and eventually, the passing of Wendel and Dale. I am grateful to have been present to share in those experiences, however hard, and am so impressed by the perspective and grace with which you have handled it all. Overall, it has been such a pleasure v being so close to all of my extended family members in Michigan, the Midwest, and across all of the United States after so many years living in Japan. The visits, vacations, and holidays we have shared together have all played a key role recharging me emotionally over the course of the marathon that is a doctoral program. Lastly, I would like to thank Zoe for her love, companionship, and patience. It has been a real and motivating joy living with you these past few years in Ann Arbor. I know we both look forward to what the future holds. vi TABLE OF CONTENTS DEDICATION ................................................................................................................................ ii ACKNOWLEDGEMENTS ........................................................................................................... iii LIST OF TABLES .......................................................................................................................... x LIST OF FIGURES ....................................................................................................................... xi ABSTRACT .................................................................................................................................. xv CHAPTER 1 Introduction............................................................................................................... 1 Actinide waste and the nuclear fuel cycle........................................................................... 2 Environmental geochemistry of actinides ........................................................................... 4 Computational methods in geochemistry............................................................................ 6 Overview of research chapters ............................................................................................ 9 References ......................................................................................................................... 14 CHAPTER 2 Quantum-mechanical investigation of the structures and energetics of uranium and plutonium incorporation into the magnetite (Fe3O4) lattice .......................................................... 22 Abstract ............................................................................................................................. 22 Introduction ....................................................................................................................... 23 Computational approach ................................................................................................... 29 The magnetite structure ............................................................................................. 29 Quantum-mechanical calculations ............................................................................. 30 Periodic solids ....................................................................................................... 31 Periodic molecules and clusters ............................................................................ 33 Frequency calculations.......................................................................................... 34 Results ..............................................................................................................................
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