Exploring the Impact of Lone Pairs on the Structural Features of Alkaline‐Earth (A) Transition‐Metal (M,M’) Chalcogenides (Q) AMM'Q₃

Abstract

Understanding electronic structures is decisive for the design of solid-state materials, as its knowledge is providing invaluable information regarding the chemical and physical properties. One aspect of steady interest in electronic structure theory is the influence of lone pairs on the structural arrangements in a given solid. Herein, we report on explorations of the impact of lone pairs on the structural features of members belonging to a prolific family of alkaline-earth-metal (A) transition-metal (M,M') chalcogenides (Q). The outcome indicates that the aspects controlling the structural preferences in the inspected AMM'Q 3type tellurides are rather subtle. In addition to the results of our first-principles-based investigations, we also provide a brief overview about the structural features for these tellurides including two new representatives which have been obtained from high-temperature solid-state reactions for the very first time.

Structural Influence of Lone Pairs in GeP2N4, a Germanium(II) Nitridophosphate

“…This feature is unprecedented in nitridophosphates, however, was theoretically investigated by Dronskowski et al. for alkaline‐earth transition‐metal chalcogenides [26] …”

“…This feature is unprecedented in nitridophosphates, however, was theoretically investigated by Dronskowski et al for alkalineearth transition-metal chalcogenides. [26] Distances trigonal pyramid (figure 3). Thus far, this coordination geometry is unprecedented in solid-state materials, which tend to form angled GeN 2 4À -units, e.g.…”

Trendbericht Festkörperchemie 2023

“…Zudem stellten sie BaCeCuTe 3 und BaDyAgTe 3 her, zwei weitere Vertreter der Reihe (Abbildung 10). 61) Anhand der isotypen Reihen in den intermetallischen Verbindungen In 1-x Sn x Pd 2 und Ga 1-x Sn x Pd 2 haben Armbrüster, Grin und Mitarbeitende untersucht, wie elektronische und geometrische Einflüsse die elektrochemische Methanoloxidation beeinflussen. 62) Die Substitution von In durch Sn diente hierbei der Variation der elektronischen Konfiguration, während die Substitution von In durch Ga die geometrischen Einflüsse aufdeckte.…”

Synthesis, crystal structure, DFT, and photovoltaic studies of BaCeCuS3

“…For instance, A or Ak atoms can be substituted by Pb/Th, and Ln atoms can be replaced by transition metals or early actinides (An), 11 which prefer octahedral coordination environments. These (A/Ak)MLnQ 3 types of structures are mainly categorized into three subtypes based on the formal oxidation state of the constituent elements: Type-I, A + M + M' 4+ (Q 2À ) 3 [M = Cu + or Ag + ; M' = Zr 4+ /Hf 4+ /Np 4+ ], 12 Type-II, Ak 2+ M + Ln 3+ (Q 2À ) 3 , 13,14 and Type-III, A 2+ M + M' 3+ (Q 2À ) 3 [M' = Sc 3+ /Y 3+ ]. 15 The electropositive A + and Ak 2+ cations in these structures mainly serve as electron donors.…”