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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 six MS 4 molecules (M = group-8 metals Fe, Ru, Os, Hs, Sm, and Pu) have been studied by using quantum-chemical density-functional and correlated wave-function approaches. The MS 4 species are compared to analogous MO 4 species recently investi-gated (Inorg. Chem. 2016, 55: 4616). Metal oxidation state (MOS) of high value VIII appears in low- spin singlet Td geometric species (Os,Hs)S 4 and (Ru,Os,Hs)O 4, whereas low MOS=II appears in high- spin septet D 2d species Fe(S 2) 2 and (slightly excited) metastable Fe(O 2) 2. The ground states of all other molecules have intermediate MOS values, containing S 2-, S 2 2-, S2 1- (and resp. O 2--, O 1-, O 2 2-, O 2 1-) ligands, bonded by ionic, covalent and correlative contributions.

Authors:
 [1]; ORCiD logo [1];  [2]; ORCiD logo [3]; ORCiD logo [4]
  1. Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing 100084 P.R. China
  2. Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing 100084 P.R. China; Physical and Theoretical Chemistry, University of Siegen, Siegen 57068 Germany
  3. Theoretical Division, Los Alamos National Laboratory, Los Alamos New Mexico 87545 USA; Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory, Richland Washington 953002 USA
  4. Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing 100084 P.R. China; Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory, Richland Washington 953002 USA
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1378013
Report Number(s):
PNNL-SA-126169
Journal ID: ISSN 0947-6539; 830403000
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
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:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Group-8 metals; Tetra-sulfides; Tetra-oxides; Oxidation states; Quantum chemistry; Relativistic effects; Electron correlation; Transition-metal chalcogenide bonding

Citation Formats

Huang, Wei, Jiang, Ning, Schwarz, W. H. Eugen, Yang, Ping, and Li, Jun. Diversity of Chemical Bonding and Oxidation States in MS 4 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 MS 4 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. Tue . "Diversity of Chemical Bonding and Oxidation States in MS 4 Molecules of Group 8 Elements". United States. doi:10.1002/chem.201701117.
@article{osti_1378013,
title = {Diversity of Chemical Bonding and Oxidation States in MS 4 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 six MS4 molecules (M = group-8 metals Fe, Ru, Os, Hs, Sm, and Pu) have been studied by using quantum-chemical density-functional and correlated wave-function approaches. The MS4 species are compared to analogous MO4 species recently investi-gated (Inorg. Chem. 2016, 55: 4616). Metal oxidation state (MOS) of high value VIII appears in low- spin singlet Td geometric species (Os,Hs)S4 and (Ru,Os,Hs)O4, whereas low MOS=II appears in high- spin septet D2d species Fe(S2)2 and (slightly excited) metastable Fe(O2)2. The ground states of all other molecules have intermediate MOS values, containing S2-, S22-, S21- (and resp. O2--, O1-, O22-, O21-) ligands, bonded by ionic, covalent and correlative contributions.},
doi = {10.1002/chem.201701117},
journal = {Chemistry - A European Journal},
issn = {0947-6539},
number = 44,
volume = 23,
place = {United States},
year = {2017},
month = {7}
}

Works referenced in this record:

Sulfur K-Edge X-ray Absorption Spectroscopy of 2Fe−2S Ferredoxin:  Covalency of the Oxidized and Reduced 2Fe Forms and Comparison to Model Complexes
journal, June 2001

  • Anxolabéhère-Mallart, Elodie; Glaser, Thorsten; Frank, Patrick
  • Journal of the American Chemical Society, Vol. 123, Issue 23
  • DOI: 10.1021/ja010472t

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Correlation consistent valence basis sets for use with the Stuttgart–Dresden–Bonn relativistic effective core potentials: The atoms Ga–Kr and In–Xe
journal, February 2001

  • Martin, Jan M. L.; Sundermann, Andreas
  • The Journal of Chemical Physics, Vol. 114, Issue 8
  • DOI: 10.1063/1.1337864

An investigation of the electronic structure of osmium tetroxide by photoelectron spectroscopy with variable photon energy
journal, December 1990


How Much Can Density Functional Approximations (DFA) Fail? The Extreme Case of the FeO 4 Species
journal, March 2016

  • Huang, Wei; Xing, Deng-Hui; Lu, Jun-Bo
  • Journal of Chemical Theory and Computation, Vol. 12, Issue 4
  • DOI: 10.1021/acs.jctc.5b01040

Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976


The d 0 , d 1 and d 2 Configurations in Known and Unknown Tetrathiometal Compounds MS 4 n - (M = Mo, Tc, Ru; W, Re, Os). A Quantum Chemical Study
journal, December 1999

  • Záliš, Stanislav; Stoll, Hermann; Baerends, Evert Jan
  • Inorganic Chemistry, Vol. 38, Issue 26
  • DOI: 10.1021/ic990891f

Coupled cluster theory for high spin, open shell reference wave functions
journal, October 1993

  • Knowles, Peter J.; Hampel, Claudia; Werner, Hans‐Joachim
  • The Journal of Chemical Physics, Vol. 99, Issue 7
  • DOI: 10.1063/1.465990

Iron-Sulfur Clusters: Nature's Modular, Multipurpose Structures
journal, August 1997


Spectroscopic Changes during a Single Turnover of Biotin Synthase:  Destruction of a [2Fe-2S] Cluster Accompanies Sulfur Insertion
journal, July 2001

  • Ugulava, Natalia B.; Sacanell, Carlos J.; Jarrett, Joseph T.
  • Biochemistry, Vol. 40, Issue 28
  • DOI: 10.1021/bi010463x

Syntheses of Ru−S Clusters with Kinetically Labile Ligands via the Photolysis of [(cymene) 3 Ru 3 S 2 ](PF 6 ) 2
journal, March 2001

  • Eckermann, Amanda L.; Fenske, Dieter; Rauchfuss, Thomas B.
  • Inorganic Chemistry, Vol. 40, Issue 7
  • DOI: 10.1021/ic0010609

R�ntgenspektren und periodisches System der Elemente
journal, December 1923


Energy-consistent relativistic pseudopotentials and correlation consistent basis sets for the 4d elements Y–Pd
journal, March 2007

  • Peterson, Kirk A.; Figgen, Detlev; Dolg, Michael
  • The Journal of Chemical Physics, Vol. 126, Issue 12
  • DOI: 10.1063/1.2647019

On the Highest Oxidation States of Metal Elements in MO 4 Molecules (M = Fe, Ru, Os, Hs, Sm, and Pu)
journal, April 2016


Energy‐adjusted pseudopotentials for the actinides. Parameter sets and test calculations for thorium and thorium monoxide
journal, May 1994

  • Küchle, W.; Dolg, M.; Stoll, H.
  • The Journal of Chemical Physics, Vol. 100, Issue 10
  • DOI: 10.1063/1.466847

Chemical Bonding in Higher Main Group Elements
journal, April 1984

  • Kutzelnigg, Werner
  • Angewandte Chemie International Edition in English, Vol. 23, Issue 4
  • DOI: 10.1002/anie.198402721

Topographical Analyses of Homonuclear Multiple Bonds between Main Group Elements
journal, July 2000


The electronic structure and properties of group 8 oxides MO4, where M=Ru, Os, and Element 108, Hs
journal, July 2001

  • Pershina, V.; Bastug, T.; Fricke, B.
  • The Journal of Chemical Physics, Vol. 115, Issue 2
  • DOI: 10.1063/1.1379579

100 Jahre Bohrsches Atommodell
journal, October 2013


Electronic spectrum of S 2 , the electron affinity of S 2 , and the binding energies of neutral and anionic S 3 clusters
journal, August 1995

  • Heinemann, Christoph; Koch, Wolfram; Lindner, Gottlieb-Georg
  • Physical Review A, Vol. 52, Issue 2
  • DOI: 10.1103/PhysRevA.52.1024

Covalency in f-element complexes
journal, January 2013

  • Neidig, Michael L.; Clark, David L.; Martin, Richard L.
  • Coordination Chemistry Reviews, Vol. 257, Issue 2
  • DOI: 10.1016/j.ccr.2012.04.029

Energy‐adjusted a b i n i t i o pseudopotentials for the first row transition elements
journal, January 1987

  • Dolg, M.; Wedig, U.; Stoll, H.
  • The Journal of Chemical Physics, Vol. 86, Issue 2
  • DOI: 10.1063/1.452288

Directionality of Hydrogen Bonds to Sulfur and Oxygen
journal, January 1996

  • Platts, J. A.; Howard, S. T.; Bracke, B. R. F.
  • Journal of the American Chemical Society, Vol. 118, Issue 11
  • DOI: 10.1021/ja952871s

Gaussian basis sets for use in correlated molecular calculations. III. The atoms aluminum through argon
journal, January 1993

  • Woon, David E.; Dunning, Thom H.
  • The Journal of Chemical Physics, Vol. 98, Issue 2
  • DOI: 10.1063/1.464303

Is Octavalent Pu(VIII) Possible? Mapping the Plutonium Oxyfluoride Series PuO n F 8–2 n ( n = 0–4)
journal, August 2015


Valence basis sets for relativistic energy-consistent small-core lanthanide pseudopotentials
journal, October 2001

  • Cao, Xiaoyan; Dolg, Michael
  • The Journal of Chemical Physics, Vol. 115, Issue 16
  • DOI: 10.1063/1.1406535

RuS2(111) Surfaces: Theoretical Study of Various Terminations and Their Interaction with H2
journal, January 1997


Electronic Structure of Rh 2 S 3 and RuS 2 , Two Very Active Hydrodesulfurization Catalysts
journal, May 1998

  • Tan, Agnes; Harris, Suzanne
  • Inorganic Chemistry, Vol. 37, Issue 9
  • DOI: 10.1021/ic971028n

Probing the Electronic Structure and Chemical Bonding of Mono-Uranium Oxides with Different Oxidation States: UO x and UO x ( x = 3–5)
journal, February 2016

  • Su, Jing; Li, Wei-Li; Lopez, Gary V.
  • The Journal of Physical Chemistry A, Vol. 120, Issue 7
  • DOI: 10.1021/acs.jpca.5b11354

Coupled-cluster theory in quantum chemistry
journal, February 2007


The Construction and Interpretation of Mcscf Wavefunctions
journal, October 1998


Refitted tetrahedral covalent radii for solids
journal, January 2012


Die chemische Bindung bei den höheren Hauptgruppenelementen
journal, April 1984


Die Oxidationsstufe, ein Dauerbrenner!
journal, March 2015


A gas-phase study of FeSn+ (n = 1-6)
journal, January 1989

  • MacMahon, T. J.; Jackson, T. C.; Freiser, Ben S.
  • Journal of the American Chemical Society, Vol. 111, Issue 2
  • DOI: 10.1021/ja00184a001

Formation of unprecedented actinidecarbon triple bonds in uranium methylidyne molecules
journal, November 2007

  • Lyon, J. T.; Hu, H. -S.; Andrews, L.
  • Proceedings of the National Academy of Sciences, Vol. 104, Issue 48
  • DOI: 10.1073/pnas.0707035104

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

100th Anniversary of Bohr’s Model of the Atom
journal, October 2013


Actinide–Silicon Multiradical Bonding: Infrared Spectra and Electronic Structures of the Si(μ-X)AnF 3 (An = Th, U; X = H, F) Molecules
journal, January 2014

  • Hu, Han-Shi; Wei, Fan; Wang, Xuefeng
  • Journal of the American Chemical Society, Vol. 136, Issue 4
  • DOI: 10.1021/ja409527u

Oxidation State, A Long-Standing Issue!
journal, March 2015


Quantum-Mechanical ab initio Investigation of the Transition-Metal Compounds OsO4, OsO3F2, OsO2F4, OsOF6, and OsF8
journal, June 1993


On the oxidation states of metal elements in MO3 - (M=V, Nb, Ta, Db, Pr, Gd, Pa) anions
journal, February 2016


Molecular Structures for FeS 4 –/0 As Determined from an ab Initio Study of the Anion Photoelectron Spectra
journal, April 2013

  • Tran, Van Tan; Hendrickx, Marc F. A.
  • The Journal of Physical Chemistry A, Vol. 117, Issue 15
  • DOI: 10.1021/jp401343j

Energy-consistent pseudopotentials and correlation consistent basis sets for the 5d elements Hf–Pt
journal, April 2009

  • Figgen, Detlev; Peterson, Kirk A.; Dolg, Michael
  • The Journal of Chemical Physics, Vol. 130, Issue 16
  • DOI: 10.1063/1.3119665

Direct FeS Cluster Involvement in Generation of a Radical in Lysine 2,3-Aminomutase
journal, December 2000

  • Cosper, Nathaniel J.; Booker, Squire J.; Ruzicka, Frank
  • Biochemistry, Vol. 39, Issue 51
  • DOI: 10.1021/bi0022184

Pentavalent Lanthanide Compounds: Formation and Characterization of Praseodymium(V) Oxides
journal, April 2016


Pentavalent lanthanide nitride-oxides: NPrO and NPrO complexes with NPr triple bonds
journal, January 2017

  • Hu, Shu-Xian; Jian, Jiwen; Su, Jing
  • Chemical Science, Vol. 8, Issue 5
  • DOI: 10.1039/C7SC00710H

The highest oxidation states of the transition metal elements
journal, March 2009


New diagnostics for coupled-cluster and Møller–Plesset perturbation theory
journal, July 1998


Ab initio study of bonding trends for f 0 actinide oxyfluoride species
journal, November 2001

  • Straka, Michal; Dyall, Kenneth G.; Pyykk�, Pekka
  • Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 106, Issue 6
  • DOI: 10.1007/s002140100295

On the existence of oxide molecules of plutonium in highest oxidation states
journal, January 2013


Relativistic effects in structural chemistry
journal, May 1988


Ab initio relativistic effective potentials with spin-orbit operators. VII. Am through element 118
journal, March 1997

  • Nash, Clinton S.; Bursten, Bruce E.; Ermler, Walter C.
  • The Journal of Chemical Physics, Vol. 106, Issue 12
  • DOI: 10.1063/1.473992

Chemical investigation of hassium (element 108)
journal, August 2002

  • Düllmann, Ch. E.; Brüchle, W.; Dressler, R.
  • Nature, Vol. 418, Issue 6900
  • DOI: 10.1038/nature00980

Optimized Slater-type basis sets for the elements 1-118
journal, May 2003

  • Van Lenthe, E.; Baerends, E. J.
  • Journal of Computational Chemistry, Vol. 24, Issue 9
  • DOI: 10.1002/jcc.10255

Oxidation States, Geometries, and Electronic Structures of Plutonium Tetroxide PuO 4 Isomers: Is Octavalent Pu Viable?
journal, November 2013

  • Huang, Wei; Xu, Wen-Hua; Su, Jing
  • Inorganic Chemistry, Vol. 52, Issue 24
  • DOI: 10.1021/ic402170q

Theoretical investigation of the effects of spin-orbit coupling on the valence photoelectron spectrum of OsO4
journal, May 1994

  • Bursten, Bruce E.; Green, Jennifer C.; Kaltsoyannis, Nikolas
  • Inorganic Chemistry, Vol. 33, Issue 11
  • DOI: 10.1021/ic00089a002

Study on iron–sulfur cluster in gas phase: electronic structure and reactivity
journal, December 1997


He-I photoelectron spectra of some d 0 transition metal compounds
journal, January 1974

  • Burroughs, Peter; Evans, Stephen; Hamnett, Andrew
  • Journal of the Chemical Society, Faraday Transactions 2, Vol. 70
  • DOI: 10.1039/f29747001895

Comparative bonding analysis of N2 and P2 versus tetrahedral N4 and P4
journal, January 2014


On the Stability and Volatility of Group 8 Tetroxides, MO 4 (M = Ruthenium, Osmium, and Hassium ( Z = 108))
journal, July 2002

  • Düllmann, Christoph E.; Eichler, Bernd; Eichler, Robert
  • The Journal of Physical Chemistry B, Vol. 106, Issue 26
  • DOI: 10.1021/jp0257146

Evolution of the structure and electronic properties of neutral and anion (n=1–7, μ=0, −1) clusters: A comprehensive analysis
journal, October 2013


Calculation of electric properties using regular approximations to relativistic effects: The polarizabilities of RuO4, OsO4, and HsO4 (Z=108)
journal, July 2003

  • Filatov, Michael; Cremer, Dieter
  • The Journal of Chemical Physics, Vol. 119, Issue 3
  • DOI: 10.1063/1.1580473

Understanding the valency of rare earths from first-principles theory
journal, June 1999

  • Strange, P.; Svane, A.; Temmerman, W. M.
  • Nature, Vol. 399, Issue 6738
  • DOI: 10.1038/21595

Bonding trends across the series of tricarbonato-actinyl anions [(AnO 2 )(CO 3 ) 3 ] 4− (An = U–Cm): the plutonium turn
journal, January 2017

  • Liu, Jian-Biao; Chen, Guo P.; Huang, Wei
  • Dalton Transactions, Vol. 46, Issue 8
  • DOI: 10.1039/C6DT03953G

Pentavalent Lanthanide Compounds: Formation and Characterization of Praseodymium(V) Oxides
journal, April 2016

  • Zhang, Qingnan; Hu, Shu-Xian; Qu, Hui
  • Angewandte Chemie International Edition, Vol. 55, Issue 24
  • DOI: 10.1002/anie.201602196

Hydrodesulfurization catalysis by transition metal sulfides
journal, February 1981


Segmented contraction scheme for small-core lanthanide pseudopotential basis sets
journal, April 2002


Relativistic regular two‐component Hamiltonians
journal, September 1993

  • Lenthe, E. van; Baerends, E. J.; Snijders, J. G.
  • The Journal of Chemical Physics, Vol. 99, Issue 6
  • DOI: 10.1063/1.466059

On structure and bonding of lanthanoid trifluorides LnF3 (Ln = La to Lu)
journal, January 2013

  • Xu, Wei; Ji, Wen-Xin; Qiu, Yi-Xiang
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 20
  • DOI: 10.1039/c3cp50717c

Infrared Spectra and Density Functional Theory Calculations of Group 8 Transition Metal Sulfide Molecules
journal, May 2009

  • Liang, Binyong; Wang, Xuefeng; Andrews, Lester
  • The Journal of Physical Chemistry A, Vol. 113, Issue 18
  • DOI: 10.1021/jp900994c

Theoretical Investigations of Geometry, Electronic Structure and Stability of UO 6 : Octahedral Uranium Hexoxide and Its Isomers
journal, August 2010

  • Xiao, Hai; Hu, Han-Shi; Schwarz, W. H. Eugen
  • The Journal of Physical Chemistry A, Vol. 114, Issue 33
  • DOI: 10.1021/jp102107n

Electronic and Structural Evolution of Monoiron Sulfur Clusters, FeS n - and FeS n ( n = 1−6), from Anion Photoelectron Spectroscopy
journal, April 2003

  • Zhai, Hua-Jin; Kiran, Boggavarapu; Wang, Lai-Sheng
  • The Journal of Physical Chemistry A, Vol. 107, Issue 16
  • DOI: 10.1021/jp027867z

Valence basis sets for relativistic energy-consistent small-core actinide pseudopotentials
journal, January 2003

  • Cao, Xiaoyan; Dolg, Michael; Stoll, Hermann
  • The Journal of Chemical Physics, Vol. 118, Issue 2
  • DOI: 10.1063/1.1521431

Energy‐adjusted a b i n i t i o pseudopotentials for the rare earth elements
journal, February 1989

  • Dolg, M.; Stoll, H.; Preuss, H.
  • The Journal of Chemical Physics, Vol. 90, Issue 3
  • DOI: 10.1063/1.456066

Segmented contraction scheme for small-core actinide pseudopotential basis sets
journal, March 2004