Ba2An(S2)2S2 (An = U, Th): Syntheses, structures, optical, and electronic properties

Adel Mesbah, Emilie Ringe, Sébastien Lebègue, Richard P Van Duyne, James A Ibers*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

23 Scopus citations

Abstract

The compounds Ba2An(S2)2S2 (An = U, Th) have been synthesized by reactions of the elements with BaS and S at 1273 and 1173 K, respectively. These isostructural compounds crystallize in a new structure type in the tetragonal space group D4h15-P4 2/nmc. The structure comprises Ba2+ cations and ∞2[An(S2)2(S)24-] layers. The An4+ cations in these layers are arranged linearly and are bridged by S2- anions. Coordination about the An center, which has symmetry 4Ì...m2, consists of two S22- ions and four S2- ions. Thus, the compounds are charge-balanced with An 4+. No other alkali-metal actinide chalcogenides are known that contain chalcogen-chalcogen bonds. Optical measurements on Ba 2Th(S2)2S2 indicate a direct band gap of 2.46(5) eV. Density functional theory calculations, performed with the HSE exchange-correlation potential, lead to band gaps of 2.2 and 1.8 eV for Ba2Th(S2)2S2 and Ba 2U(S2)2S2, respectively, thus demonstrating the utility of applying this functional to 5f-electron systems.

Original languageEnglish (US)
Pages (from-to)13390-13395
Number of pages6
JournalInorganic Chemistry
Volume51
Issue number24
DOIs
StatePublished - Dec 17 2012

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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