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Rationalizing Th Structures of Zintl and Polar Intermetallic Phases Fei Wang Iowa State University

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Rationalizing Th Structures of Zintl and Polar Intermetallic Phases Fei Wang Iowa State University Iowa State University Capstones, Theses and Graduate Theses and Dissertations Dissertations 2011 Rationalizing th structures of Zintl and polar intermetallic phases Fei Wang Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/etd Part of the Chemistry Commons Recommended Citation Wang, Fei, "Rationalizing th structures of Zintl and polar intermetallic phases" (2011). Graduate Theses and Dissertations. 11943. https://lib.dr.iastate.edu/etd/11943 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Graduate Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. Rationalizing the structures of Zintl and polar intermetallic phases by Fei Wang A dissertation submitted to the graduate faculty in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Major: Inorganic Chemistry Program of Study Committee: Gordon J. Miller, Major Professor John D. Corbett Mark S. Gordon Vitalij K. Pecharsky Patricia A. Thiel Iowa State University Ames, Iowa 2011 Copyright © Fei Wang, 2011. All rights reserved. ii Dedicated to Mom and Dad. iii TABLE OF CONTENTS Acknowledgement ........................................................................................................................... v Chapter 1. Introduction ................................................................................................................... 1 1.1 The Specialties of Zintl and Polar Intermetallic Phases .......................................................... 1 1.2 Zintl-Klemm Formalism – Success and Limitations .............................................................. 2 1.3 Rationalizing Structures with Quantum Mechanical Calculations .......................................... 4 1.4 Handling the Coloring Problem ............................................................................................. 6 1.5 Layout of the Dissertation ..................................................................................................... 7 1.6 References ............................................................................................................................. 8 Chapter 2. Experimental and Computational Techniques, in General ............................................ 11 2.1 Syntheses ............................................................................................................................ 11 2.2 Characterization .................................................................................................................. 11 2.3 Computations ..................................................................................................................... 12 2.4 References .......................................................................................................................... 13 Chapter 3. Revisiting the Zintl-Klemm Concept I: Alkali Metal Trielides ..................................... 15 3.1 Abstract .............................................................................................................................. 15 3.2 Introduction ........................................................................................................................ 15 3.3 Computational Details ........................................................................................................ 20 3.4 Results and Discussions ...................................................................................................... 25 3.5 Conclusions ........................................................................................................................ 40 3.6 Acknowledgements ............................................................................................................. 41 3.7 References .......................................................................................................................... 41 3.8 Supporting Information ....................................................................................................... 46 Chapter 4. Revisiting the Zintl-Klemm Concept II: A2AuBi ( A = Alkali Metals) ........................... 56 4.1 Abstract .............................................................................................................................. 56 4.2 Introduction ........................................................................................................................ 56 4.3 Computational Details ........................................................................................................ 58 4.4 Results and Discussions ...................................................................................................... 60 4.5 Conclusions ........................................................................................................................ 73 4.6 Acknowledgements ............................................................................................................. 73 4.7 References .......................................................................................................................... 73 4.8 Supporting Information ....................................................................................................... 76 iv Chapter 5. EuAg xAl 11-x with the BaCd 11 -Type Structure: Phase Width, Coloring, and Electronic Structure ........................................................................................................................ 78 5.1 Abstract .............................................................................................................................. 78 5.2 Introduction ........................................................................................................................ 78 5.3 Experiments ........................................................................................................................ 80 5.4 Results and Discussions ...................................................................................................... 82 5.5 Conclusions ........................................................................................................................ 91 5.6 Acknowledgements ............................................................................................................. 91 5.7 References .......................................................................................................................... 91 5.8 Supporting Information ....................................................................................................... 94 Chapter 6. EuAg xAl 11-x with the BaHg 11 -Type Structure: Composition, Coloring, and Competition with the BaCd 11 -Type Structure ................................................................................ 103 6.1 Abstract ............................................................................................................................ 103 6.2 Introduction ...................................................................................................................... 103 6.3 Experiments ...................................................................................................................... 105 6.4 Results and Discussions .................................................................................................... 107 6.5 Conclusions ...................................................................................................................... 118 6.6 Acknowledgements ........................................................................................................... 118 6.7 References ........................................................................................................................ 119 6.8 Supporting Information ..................................................................................................... 122 Chapter 7. Stacking Polymorphs in Gd 5Si 4, Gd 5Ge 4, and Gd 5Si 2Bi 2: A Computational Investigation ................................................................................................................................ 132 7.1 Introduction ...................................................................................................................... 132 7.2 Computational Details ...................................................................................................... 133 7.3 Results and Discussions .................................................................................................... 135 7.4 Conclusions ...................................................................................................................... 139 7.5 References ........................................................................................................................ 140 Chapter 8. Conclusions and Future Work .................................................................................... 142 v Acknowledgement Upon the completion of my graduate study, I would really like to show my gratitude to my teachers, colleagues, and friends who made my time in Iowa State University a lifelong memory. First of all, I shall thank my major professor, Dr. Gordon J. Miller. His expertise in solid state chemistry and patience in helping students make him an exemplary mentor. I have learned
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