Premium
Regular [Tl 6 ] 6– Cluster in Cs 4 Tl 2 O Exhibiting Closed‐Shell Configuration and Energetic Stabilization due to Relativistic Spin–Orbit Coupling
Author(s) -
Saltykov Vyacheslav,
Nuss Jürgen,
Wedig Ulrich,
Jansen Martin
Publication year - 2011
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201000405
Subject(s) - octahedron , crystallography , coupling (piping) , physics , open shell , atomic physics , spin (aerodynamics) , spin–orbit interaction , crystal structure , chemistry , condensed matter physics , materials science , metallurgy , thermodynamics
Cs 4 Tl 2 O was synthesized by reaction of the binary compounds CsTl and Cs 2 O at 573 K, followed by slow cooling to room temperature. According to single‐crystal X‐ray analysis, the title compound crystallizes in a new structure type (trigonal, space group R $\bar{3}$ m (no. 166), a = 11.986(1), c = 20.370(2) Å, Z = 9). It consists of isolated [Tl 6 ] 6– octahedra, being regular with respect to the equality of all three main diagonals (4.546(5) Å), and of [Cs 12 O 3 ] 6+ triple octahedra extending along the c direction.The electronic structure of Cs 4 Tl 2 O was examined by relativistic density functional calculations including spin–orbit coupling and compared to the one of Rb 10 Tl 6 O 2 , which exhibits a highly distorted [Tl 6 ] 6– octahedra. In the latter case the closed‐shell electronic structure is the result of a Jahn–Teller distortion. In contrast, the regular one in Cs 4 Tl 2 O corresponds to a closed‐shell configuration, in accordance with diamagnetic properties, only if spin–orbit coupling is considered.