Electronic Stabilization in Metal-Rich Solid-State Phases
Program Scope: The program seeks to expand our knowledge and understanding of solid-state chemistry by combining experiment—particularly exploratory synthesis and structure—with theory in order to uncover new families of intermetallic phases and to understand the factors that stabilize both new and known phases. These families include Zintl, cluster, Hume-Rothery, quasicrystalline, and related phases. Experiments encompass high temperature synthesis (arc melting, reactive metal fluxes, sealed metal container) and variable-temperature single crystal and powder diffraction. Theoretical efforts span first-principles to semi-empirical calculations.
Major Program Achievements: We have explored, developed and organized new areas of polar intermetallics formed between active metals and the triels (Ga, In, Tl) as well as Mg, Li, Au, discovering much unique chemistry beyond the classical Zintl (valence) boundary. We synthesized and characterized new Zintl (valence) and related compounds: K39In80, K5InPb8, a Bergman-type structure in Na11(Cd,Tl)27, and new hyper-electronic networks (SrIn4, Sr3In5, KAu4In2, BaMg5In3) with relatively low numbers of cations. We identified and interpreted electronic deviations from Zintl concepts in terms of structure, properties, and theory, i.e., the importance of atom size limitations in the stability of certain classical structure types and of electronic tuning via Li, Mg, Zn, etc. substitutions in triel networks,. New e-poorer intermetallic phases exhibiting important relativistic effects were defined for the substituted triel phases Ba2AuTl7, Sr2PtTl2, BaAuIn3, and BaAu2In2. Five problem cases have been studied by ab-initio methods, demonstrating the absence of the closed shell (Zintl) anions Pb–4, Bi–3 and Ge2–6 in certain salts and the major role of sodium in the bonding in Na3AuIn2, Na6TlSb4 and KNa3In9. We refined a new series of binary Hume-Rothery-type intermetallics in the Zn-Pd system that provide greater insights into the stability of cubic gamma-brass structures, their relationships to quasicrystals, and some general aspects of the influence of electronic structure on complex intergrowth structures. Zn1-xPdx (0.15 ≤ x ≤ 0.25) were prepared (see also Bulk Structures) with six structures identified. Electronic structures show pseudogaps at the corresponding Fermi levels, with these features driven by Zn-Pd and Zn-Zn orbital interactions. Specific site preferences exist for Pd at the center of Zn-rich icosahedra, which can also be understood from theoretical calculations as well. Subsequent structural characterization of Cu–Zn gamma brasses by neutron diffraction identified a constant [Zn4Cu4] kernel for the whole composition range. This work suggests a chemical (real space) interpretation for the stability ranges of gamma brasses.
Program Impact: Our discoveries have impacted or motivated solid-state chemistry concepts and programs around the world and have correspondingly attracted students and visitors from many places. This impact includes groups utilizing a combination of experiment and theory to investigate problems in solid-state chemistry, as well as in thorough characterization of products beyond crystal structure determinations.
Contact Information:
John Corbett
Selected Publications
| Shengfeng Liu and John D. Corbett, "Ba 2 AuTl 7 : An Intermetallic Compound with a Novel Condensed Structure", Inorg. Chem. 43 , 2471-2473 (2004). (Communication). | Reprint |
| A.-V. Mudring and J. D. Corbett, "Unusual Electronic and Bonding Properties of the Zintl Phase Ca5Ge3 and Related Compounds. A Theoretical Analysis," J. Am. Chem. Soc. , 126 , 5277-5281 (2004). | |
| Bin Li and John D. Corbett, "Synthesis, Structure, and Characterization of a New Cubic Mixed Cluster Phase Na13(Cd0.70 Tl0.30 )27 of the Bergman Type," Inorg. Chem . 43 , 3582-3587 (2004). | Reprint |
| Shengfeng Liu and John D. Corbett, "Synthesis, Structure and Bonding of BaAuIn3 and BaAuTl3 -Stabilization of BaAl4 -Type Examples Through Gold Substitution", Inorg. Chem. 43 , 4988-4993 (2004). | Reprint |
| Michael T. Klem and John D. Corbett, "Synthesis, Structure, and Bonding of the Nonclassical Zintl Phase K5As3Pb3 ", Inorg. Chem. 43 , 5501-5504 (2004). | Reprint |
| Anja-Verena Mudring and John D. Corbett", "Influence of Cations on Physical Properties of the Zintl Phases", Z. Anorg. Allg. Chem. 630 , 1746 (2004). | |
| Niels Gerlitzki, Gerd Meyer, Anja-Verena Mudring, John Corbett, "Praseodymium Diiodide, PrI 2 , Revisited by Synthesis, Structure Determination, and Theory", J. Alloys Compd. 300 , 211-218 (2004). | |
| B. Li and J. D. Corbett, "Phase Stabilization through Electronic Tuning: Electron-Poorer Alkali-Metal-Indium Compounds with Unprecedented In/Li Clusters", J. Am. Chem. Soc., 127, 926-932 (2005). | |
| Arnold Guloy and John D. Corbett, "Syntheses and Structure of the La5Ge3 Z Phases (Z = Si, Sn, Pb, Ga, In). Structural Relationships among the M5X4 -Type Structures", J. Solid State Chem. , 178, 1112-1124 (2005). | Reprint |
| Michael T. Klem and John D. Corbett, "A5InPb8 (A = K, Rb): An Apparent Zintl phase with Lead Tetrahedra Interbridged by : 6-In Atoms", Inorg. Chem ., 44, 5990-5995 (2005). | Reprint |
| Anja-V. Mudring and John D. Corbett, "Importance of Cations in the Properties of Zintl Phases. The Electronic Structure of Na6TlSb4 ", Inorg. Chem. 44, 5636-5640 (2005). | Reprint |
| Bin Li and John D. Corbett, "Participation of Sodium in the Bonding of Anionic Networks: Synthesis, Structure and Bonding of Na3MIn2 (M = Au, Ag)", Inorg. Chem. 44, 6515-6517 (2005) (Communication) | Reprint |
| Ashok K. Ganguli, Shalabh Gupta, Jing-Tae Zhao, E. Alejandro Leon-Escamilla, and John D. Corbett, " Inherent Instabilities of Some W5Si3 -Type Binary Phases with Larger Active Metal Atoms. Six Examples in the Ba-Pb, Ca-Sn-Mg,Cu,Zn, and La-Ga-Al,Zn Systems", J. Solid State Chem. 178, 2959-2972 (2005). | Reprint |
| Bin Li and John D. Corbett, "Synthesis, Structure and Bonding of Rb14(Mg1- xInx )30 . A Nonstoichiometric Phase with an Unusual Substitution in the Anion Fragment", Inorg. Chem. 45, 156-161 (2006). | Reprint |
| Ashok K.Ganguli, Shalabh Gupta, and John D. Corbett, "A New Tetragonal Structure Type for A2Ca10Sb9(A = Li, Mg). Electronic Variability around a Zintl Phase", Inorg. Chem. 45, 196-200 (2006). | Reprint |
| Shengfeng Liu and John D. Corbett, " Synthesis, Structure, and Properties of Four Ternary Compounds: CaSr Tt, Tt = Si, Ge, Sn, Pb", J. Solid State Chem. 830-835 (2006). | Reprint |
| Jing-Cao Dai and John D. Corbett, "Substitution of Au or Hg into BaTl2 and BaIn2. New Ternary Examples of Smaller CeCu 2 -Type Intermetallic Phases", Inorg. Chem . 45, 2104- 2111 (2006). | Reprint |
| Bin Li and John D. Corbett, "Electronic Structures of KNa3In9 and Na2In, Two Metallic Phases with Classical Closed Shell Electronic Configurations", Inorg. Chem., 45, 2960- 2964 (2006). | Reprint |
| Bin Li and John D. Corbett, "Synthesis and Structure of K3Mg20In14 , a Stuffed Variant of the BaHg11 Structure Type with a Magnesium-Indium Network", Inorg. Chem., 45 , 3861-3863 (2006) (Communication). | Reprint |
| John D. Corbett, "Exploratory Synthesis of Reduced Rare-Earth-Metal Halides, Chalcogenides, Intermetallics. New Compounds, Structure, and Properties", J. Alloys Compd. 418, 1-20 (2006). (Spedding Award Address). | |
| Bin Li and John D. Corbett "Intermetallic Compounds with 1D Infinite Tunnels. Syntheses and Structures of AAu4In2(A = K, Rb)", J. Am. Chem. Soc., 128, 12392-3 (2006) (Communication). | |
| E. Alejandro Leon-Escamilla and John D. Corbett "Hydrogen in Polar Intermetallics. Binary Pnictides of Divalent Metals with Mn5Si3-type Structures and Their Isotypic Ternary Hydride Solutions", Chem. Mat. 18, 4782-4792 (2006). | |
Bin Li and John D. Corbett, "Electronic Stabilization Effects. Three New K-In-T (T = Mg, Au, Zn) Network Compounds", Inorg. Chem. 45 , 8958-8964 (2006). |
Reprint |
| Bin Li and John D. Corbett, " AeMg5In3(Ae = Ba, Sr): Intermetallic Compounds with Well-Differentiated Roles for the Normal Cation Types", Inorg. Chem., 46, accepted (2007) | |
| O. Gourdon, S.L. Bud'ko, D. Williams, G.J. Miller, "Crystallographic, Electronic and Magnetic Studies of Gamma2-GaM (M = Cr, Mn, or Fe): From Antiferromagnetism to Ferromagnetism," Inorg. Chem. 2004, 43 , 3210-3218. | Reprint |
| D. Gout, E. Benbow, O. Gourdon, G.J. Miller, G. J., "Composition-Structure Relationships in Polar Intermetallics: Experimental and Theoretical Studies of LaNi1+xAl6 - x(x = 0.44)," Inorg. Chem. , 2004 , 43 , 4604-4609. | Reprint |
| D. Gout, T.J. Barker, O. Gourdon, G.J. Miller, "A New Superstructure for the BaAl4 -Structure Type: An Experimental and Theoretical Study of La2NiAl7 ," Chem. Mater. 2005 , 17 , 3661-3667. | |
O. Gourdon, D. Gout, and G. J. Miller, "Electronic states of intermetallic compounds," Encyclopedia of Condensed Matter Physics , G. Bassani, G. Liedl, and P. Wyder, editors. (Elsevier, Amsterdam, Netherlands, 2005 ), pp. 409-422. |
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| O. Gourdon, Z. Izaola, L. Elcoro, V. Petricek, and G. J. Miller, "Zn1 - x Pdx( x = 0.14 to 0.24): A missing link between intergrowth compounds and quasicrystal approximants," Philos. Mag. 2006 , 86 , 419-426. | |
| O. Gourdon, and G. J. Miller, "Intergrowth Compounds in the Zn-rich Zn-Pd System: Towards 1D Quasicrystal Approximants," Chem. Mater. 2006 , 18 , 1848-1856. | |
| G. J. Miller, "The Coloring Problem in Solids: Implications for Structures and Properties," Z. Anorg. Allg. Chem. 2006 , 632 , 2078. | |
O. Gourdon, D. Gout, D. J. Williams, T. Proffen, S. Hobbs, G. J. Miller, "Atomic Distributions in the gamma -Brass Structure of the Cu-Zn System: A Structural and Theoretical Study," Inorg. Chem. 2007 , in press. |
Materials Chemistry and
Biomolecular Materials Program
Ames Laboratory
Iowa State University
142 Spedding Hall
Ames, IA 50011 USA
Phone: 1.515.294.7568
FAX: 1.515.294.4709
