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Electronic Structures of Polar Intermetallic Compounds

A special issue of Materials (ISSN 1996-1944). This special issue belongs to the section "Advanced Materials Characterization".

Deadline for manuscript submissions: closed (30 October 2021) | Viewed by 5314

Special Issue Editor


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Guest Editor
Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, D-52074 Aachen, Germany
Interests: solid-state chemistry; polar intermetallic compounds; crystal structure; materials properties; nature of bonding; quantum chemistry

Special Issue Information

Dear Colleagues,

In light of the growing demand for materials addressing future challenges, there is a critical need to design solid-state materials that meet the respective task-specific requirements. To do so, it is mandatory to understand the electronic structure of a given solid-state material because the knowledge of the electronic structure of given solid-state compound provides conclusive information about its chemical and physical properties. Furthermore, investigating the electronic structures of previously unknown materials, which is the workhorse of today´s computational materials design, allows the acceleration of the discoveries of unprecedented compounds of interest. To accomplish the tailored design of materials, diverse experimental as well as quantum-chemical means have meanwhile been made available to the multidisciplinary community of materials scientists.

In the quest for new materials, previous explorative efforts that have employed both experimental and quantum-chemical means determined a unique group of solid-state materials dubbed as "polar intermetallic compounds". The crystal structures of these intermetallics are typically composed of polycationic or polyanionic fragments combined with monoatomic counterions, while their electronic structures cannot be understood by applying traditional valence-electron rules. In the present Special Issue, prototypical examples of the group of polar intermetallics are presented to demonstrate the unique kind of electronic structures.

Dr. Simon Steinberg
Guest Editor

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Keywords

  • polar intermetallic compounds
  • electronic structures
  • chemical bonding
  • crystal structures

Published Papers (2 papers)

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Research

13 pages, 2932 KiB  
Article
The Role of Different Alkali Metals in the A15Tl27 Type Structure and the Synthesis and X-ray Structure Analysis of a New Substitutional Variant Cs14.53Tl28.4
by Vanessa F. Schwinghammer, Susanne M. Tiefenthaler and Stefanie Gärtner
Materials 2021, 14(24), 7512; https://doi.org/10.3390/ma14247512 - 8 Dec 2021
Cited by 3 | Viewed by 2219
Abstract
Alkali metal thallides have been known since the report of E. Zintl on NaTl in 1932. Subsequently, binary and ternary thallides of alkali metals have been characterized. At an alkali metal proportion of approximately 33% (A:Tl~1:2, A = alkali metal), three different unique [...] Read more.
Alkali metal thallides have been known since the report of E. Zintl on NaTl in 1932. Subsequently, binary and ternary thallides of alkali metals have been characterized. At an alkali metal proportion of approximately 33% (A:Tl~1:2, A = alkali metal), three different unique type structures are reported: K49Tl108, Rb17Tl41 and A15Tl27 (A = Rb, Cs). Whereas Rb17Tl41 and K49Tl108 feature a three-dimensional sublattice of Tl atoms, the A15Tl27 structure type includes isolated Tl11 clusters as well as two-dimensional Tl-layers. This unique arrangement is only known so far when the heavier alkali metals Rb and Cs are included. In our contribution, we present single-crystal X-ray structure analyses of new ternary and quaternary compounds of the A15Tl27 type structure, which include different amounts of potassium. The crystal structures allow for the discussion of the favored alkali metal for each of the four Wyckoff positions and clearly demonstrate alkali metal dependent site preferences. Thereby, the compound Cs2.27K12.73Tl27 unambiguously proves the possibility of a potassium-rich A15Tl27 phase, even though a small amount of cesium appears to be needed for the stabilization of the latter structure type. Furthermore, we also present two compounds that show an embedding of Tl instead of alkali metal into the two-dimensional substructure, being equivalent to the formal oxidation of the latter. Cs14.53Tl28.4 represents the binary compound with the so far largest proportion of incorporated Tl in the structure type A15Tl27. Full article
(This article belongs to the Special Issue Electronic Structures of Polar Intermetallic Compounds)
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12 pages, 2023 KiB  
Article
Probing the Validity of the Zintl−Klemm Concept for Alkaline-Metal Copper Tellurides by Means of Quantum-Chemical Techniques
by Sabrina Smid and Simon Steinberg
Materials 2020, 13(9), 2178; https://doi.org/10.3390/ma13092178 - 9 May 2020
Cited by 12 | Viewed by 2369
Abstract
Understanding the nature of bonding in solid-state materials is of great interest for their designs, because the bonding nature influences the structural preferences and chemical as well as physical properties of solids. In the cases of tellurides, the distributions of valence-electrons are typically [...] Read more.
Understanding the nature of bonding in solid-state materials is of great interest for their designs, because the bonding nature influences the structural preferences and chemical as well as physical properties of solids. In the cases of tellurides, the distributions of valence-electrons are typically described by applying the Zintl−Klemm concept. Yet, do these Zintl−Klemm treatments provide adequate pictures that help us understanding the bonding nature in tellurides? To answer this question, we followed up with quantum-chemical examinations on the electronic structures and the bonding nature of three alkaline-metal copper tellurides, i.e., NaCu3Te2, K2Cu2Te5, and K2Cu5Te5. In doing so, we accordingly probed the validity of the Zintl−Klemm concept for these ternary tellurides, based on analyses of the respective projected crystal orbital Hamilton populations (−pCOHP) and Mulliken as well as Löwdin charges. Since all of the inspected tellurides are expected to comprise Cu−Cu interactions, we also paid particular attention to the possible presence of closed-shell interactions. Full article
(This article belongs to the Special Issue Electronic Structures of Polar Intermetallic Compounds)
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