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Title: Diversity of Chemical Bonding and Oxidation States in MS 4 Molecules of Group 8 Elements

Abstract

The geometric and electronic ground-state structures of 30 isomers of six MS 4 molecules (M=Group 8 metals Fe, Ru, Os, Hs, Sm, and Pu) have been examined by using quantum-chemical density functional theory and correlated wavefunction approaches. The MS 4 species were compared to analogous MO 4 species recently investigated (W. Huang, W.-H. Xu, W. H. E. Schwarz, J. Li, Inorg. Chem. 2016, 55, 4616). A metal oxidation state (MOS) with a high value of eight appeared in the low-spin singlet Td geometric species (Os,Hs)S 4 and (Ru,Os,Hs)O 4, whereas a low MOS of two appeared in the high-spin septet D2d species Fe(S 2) 2 and (slightly excited) metastable Fe(O 2) 2. The ground states of all other molecules had intermediate MOS values, with S 2₋, S 2 2₋, S 2 1₋ (and O 2₋, O 1₋, O 2 2₋, O 2 1₋) ligands bonded by ionic, covalent, and correlative contributions. The known tendencies toward lower MOS on going from oxides to sulfides, from Hs to Os to Ru, and from Pu to Sm, and the specific behavior of Fe, were found to arise from the different atomic orbital energies and radii of the ( n₋1)p core and ( n₋1)dmore » and ( n₋2)f valence shells of the metal atoms in row n of the periodic table. The comparative results of the electronic and geometric structures of the MO 4 and MS 4 species displays insight into the periodicity of oxidation states and bonding.« less

Authors:
 [1]; ORCiD logo [1];  [2]; ORCiD logo [3]; ORCiD logo [4]
  1. Tsinghua Univ., Beijing (China)
  2. Tsinghua Univ., Beijing (China); Univ. of Siegen, Siegen (Germany)
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  4. Tsinghua Univ., Beijing (China); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC). Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1512731
Report Number(s):
LA-UR-17-22055
Journal ID: ISSN 0947-6539
Grant/Contract Number:  
89233218CNA000001
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 23; Journal Issue: 44; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
chalcogenides; electron correlation; group 8 elements; oxidation; quantum chemistry; relativistic effects

Citation Formats

Huang, Wei, Jiang, Ning, Schwarz, W. H. Eugen, Yang, Ping, and Li, Jun. Diversity of Chemical Bonding and Oxidation States in MS4 Molecules of Group 8 Elements. United States: N. p., 2017. Web. doi:10.1002/chem.201701117.
Huang, Wei, Jiang, Ning, Schwarz, W. H. Eugen, Yang, Ping, & Li, Jun. Diversity of Chemical Bonding and Oxidation States in MS4 Molecules of Group 8 Elements. United States. doi:10.1002/chem.201701117.
Huang, Wei, Jiang, Ning, Schwarz, W. H. Eugen, Yang, Ping, and Li, Jun. Wed . "Diversity of Chemical Bonding and Oxidation States in MS4 Molecules of Group 8 Elements". United States. doi:10.1002/chem.201701117. https://www.osti.gov/servlets/purl/1512731.
@article{osti_1512731,
title = {Diversity of Chemical Bonding and Oxidation States in MS4 Molecules of Group 8 Elements},
author = {Huang, Wei and Jiang, Ning and Schwarz, W. H. Eugen and Yang, Ping and Li, Jun},
abstractNote = {The geometric and electronic ground-state structures of 30 isomers of six MS4 molecules (M=Group 8 metals Fe, Ru, Os, Hs, Sm, and Pu) have been examined by using quantum-chemical density functional theory and correlated wavefunction approaches. The MS4 species were compared to analogous MO4 species recently investigated (W. Huang, W.-H. Xu, W. H. E. Schwarz, J. Li, Inorg. Chem. 2016, 55, 4616). A metal oxidation state (MOS) with a high value of eight appeared in the low-spin singlet Td geometric species (Os,Hs)S4 and (Ru,Os,Hs)O4, whereas a low MOS of two appeared in the high-spin septet D2d species Fe(S2)2 and (slightly excited) metastable Fe(O2)2. The ground states of all other molecules had intermediate MOS values, with S2₋, S22₋, S21₋ (and O2₋, O1₋, O22₋, O21₋) ligands bonded by ionic, covalent, and correlative contributions. The known tendencies toward lower MOS on going from oxides to sulfides, from Hs to Os to Ru, and from Pu to Sm, and the specific behavior of Fe, were found to arise from the different atomic orbital energies and radii of the (n₋1)p core and (n₋1)d and (n₋2)f valence shells of the metal atoms in row n of the periodic table. The comparative results of the electronic and geometric structures of the MO4 and MS4 species displays insight into the periodicity of oxidation states and bonding.},
doi = {10.1002/chem.201701117},
journal = {Chemistry - A European Journal},
number = 44,
volume = 23,
place = {United States},
year = {2017},
month = {5}
}

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