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

doi:10.1021/ic302223m

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 journal › Article › peer-review

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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)₂^4-] layers. The An⁴⁺ cations in these layers are arranged linearly and are bridged by S^2- anions. Coordination about the An center, which has symmetry 4Ì...m2, consists of two S₂^2- ions and four S^2- 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 language	English (US)
Pages (from-to)	13390-13395
Number of pages	6
Journal	Inorganic chemistry
Volume	51
Issue number	24
DOIs	https://doi.org/10.1021/ic302223m
State	Published - Dec 17 2012

ASJC Scopus subject areas

Inorganic Chemistry
Physical and Theoretical Chemistry

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

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 4{\`I}...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.",

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AU - Ibers, James A.

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N2 - 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.

AB - 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.

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

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