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Title: Electronic structures and water reactivity of mixed metal sulfide cluster anions

The electronic structures and chemical reactivity of the mixed metal sulfide cluster anion (MoWS{sub 4}{sup −}) have been investigated with density functional theory. Our study reveals the presence of two almost isoenergetic structural isomers, both containing two bridging sulfur atoms in a quartet state. However, the arrangement of the terminal sulfur atoms is different in the two isomers. In one isomer, the two metals are in the same oxidation state (each attached to one terminal S). In the second isomer, the two metals are in different oxidation states (with W in the higher oxidation state attached to both terminal S). The reactivity of water with the two lowest energy isomers has also been studied, with an emphasis on pathways leading to H{sub 2} release. The reactive behavior of the two isomers is different though the overall barriers in both systems are small. The origin of the differences are analyzed and discussed. The reaction pathways and barriers are compared with the corresponding behavior of monometallic sulfides (Mo{sub 2}S{sub 4}{sup −} and W{sub 2}S{sub 4}{sup −}) as well as mixed metal oxides (MoWO{sub 4}{sup −})
Authors:
;  [1]
  1. Department of Chemistry, Indiana University, Bloomington, Indiana 47405 (United States)
Publication Date:
OSTI Identifier:
22420047
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 7; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANIONS; ATOMS; COMPARATIVE EVALUATIONS; DENSITY FUNCTIONAL METHOD; ELECTRONIC STRUCTURE; HYDROGEN; ISOMERS; METALS; OXIDES; REACTIVITY; SULFIDES; SULFUR; WATER