Spin-Polarization-Induced Preedge Transitions in the Sulfur K-Edge XAS Spectra of Open-Shell Transition-Metal Sulfates: Spectroscopic Validation of σ-Bond Electron Transfer

Frank, Patrick; Szilagyi, Robert K.; Gramlich, Volker; Hsu, Hua-Fen; Hedman, Britt; Hodgson, Keith O.

doi:10.1021/acs.inorgchem.6b00991

Title: Spin-Polarization-Induced Preedge Transitions in the Sulfur K-Edge XAS Spectra of Open-Shell Transition-Metal Sulfates: Spectroscopic Validation of σ-Bond Electron Transfer

Journal Article · Mon Jan 09 00:00:00 EST 2017 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.6b00991· OSTI ID:1353168

^[1]; Szilagyi, Robert K. ^[2]; Gramlich, Volker ^[3]; Hsu, Hua-Fen ^[4]; Hedman, Britt ^[5]; Hodgson, Keith O. ^[6]

Stanford Univ., CA (United States). Dept. of Chemistry; SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Montana State Univ., Bozeman, MT (United States). Dept. of Chemistry and Biochemistry; Momentum Chemical Structure-Function Lab., Budapest (Hungary)
Federal Inst. of Technology, Zurich (Switzerland). ETH-Zentrum, Lab. fuer Kristallographie
National Cheng-Kung Univ., Tainan City (Taiwan). Dept. of Chemistry
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Stanford Univ., CA (United States). Dept. of Chemistry; SLAC National Accelerator Lab., Menlo Park, CA (United States)

Sulfur K-edge X-ray absorption spectroscopy (XAS) spectra of the monodentate sulfate complexes [M^II(itao)(SO₄)(H₂O)_0,1] (M = Co, Ni, Cu) and [Cu(Me₆tren)(SO₄)] exhibit well-defined preedge transitions at 2479.4, 2479.9, 2478.4, and 2477.7 eV, respectively, despite having no direct metal–sulfur bond, while the XAS preedge of [Zn(itao)(SO₄)] is featureless. The sulfur K-edge XAS of [Cu(itao)(SO₄)] but not of [Cu(Me₆tren)(SO₄)] uniquely exhibits a weak transition at 2472.1 eV, an extraordinary 8.7 eV below the first inflection of the rising K-edge. Preedge transitions also appear in the sulfur K-edge XAS of crystalline [M^II(SO₄)(H₂O)] (M = Fe, Co, Ni, and Cu, but not Zn) and in sulfates of higher-valent early transition metals. Ground-state density functional theory (DFT) and time-dependent DFT (TDDFT) calculations show that charge transfer from coordinated sulfate to paramagnetic late transition metals produces spin polarization that differentially mixes the spin-up (α) and spin-down (β) spin orbitals of the sulfate ligand, inducing negative spin density at the sulfate sulfur. Ground-state DFT calculations show that sulfur 3p character then mixes into metal 4s and 4p valence orbitals and various combinations of ligand antibonding orbitals, producing measurable sulfur XAS transitions. TDDFT calculations confirm the presence of XAS preedge features 0.5–2 eV below the rising sulfur K-edge energy. The 2472.1 eV feature arises when orbitals at lower energy than the frontier occupied orbitals with S 3p character mix with the copper(II) electron hole. Transmission of spin polarization and thus of radical character through several bonds between the sulfur and electron hole provides a new mechanism for the counterintuitive appearance of preedge transitions in the XAS spectra of transition-metal oxoanion ligands in the absence of any direct metal–absorber bond. The 2472.1 eV transition is evidence for further radicalization from copper(II), which extends across a hydrogen-bond bridge between sulfate and the itao ligand and involves orbitals at energies below the frontier set. In conclusion, this electronic structure feature provides a direct spectroscopic confirmation of the through-bond electron-transfer mechanism of redox-active metalloproteins.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER); National Institutes of Health (NIH)

Grant/Contract Number:: P41GM103393; AC02-76SF00515

OSTI ID:: 1353168

Journal Information:: Inorganic Chemistry, Vol. 56, Issue 3; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 6 works

Citation information provided by
Web of Science

References (66)

Ligand K-Edge X-ray Absorption Spectroscopy as a Probe of Ligand-Metal Bonding: Charge Donation and Covalency in Copper-Chloride Systems Shadle, Susan E.; Hedman, Britt; Hodgson, Keith O. Inorganic Chemistry, Vol. 33, Issue 19 https://doi.org/10.1021/ic00097a009	journal	September 1994
Ligand K-edge x-ray absorption spectroscopic studies: metal-ligand covalency in a series of transition metal tetrachlorides Shadle, Susan E.; Hedman, Britt; Hodgson, Keith O. Journal of the American Chemical Society, Vol. 117, Issue 8 https://doi.org/10.1021/ja00113a015	journal	March 1995
A Quantitative Description of the Ground-State Wave Function of Cu _A by X-ray Absorption Spectroscopy: Comparison to Plastocyanin and Relevance to Electron Transfer DeBeer George, Serena; Metz, Markus; Szilagyi, Robert K. Journal of the American Chemical Society, Vol. 123, Issue 24 https://doi.org/10.1021/ja004109i	journal	June 2001
Sulfur K-Edge X-ray Absorption Spectroscopy as a Probe of Ligand−Metal Bond Covalency: Metal vs Ligand Oxidation in Copper and Nickel Dithiolene Complexes Sarangi, Ritimukta; DeBeer George, Serena; Rudd, Deanne Jackson Journal of the American Chemical Society, Vol. 129, Issue 8 https://doi.org/10.1021/ja0665949	journal	February 2007
Ligand K-edge X-ray absorption spectroscopy: covalency of ligand–metal bonds Solomon, Edward I.; Hedman, Britt; Hodgson, Keith O. Coordination Chemistry Reviews, Vol. 249, Issue 1-2 https://doi.org/10.1016/j.ccr.2004.03.020	journal	January 2005
Calibration of Scalar Relativistic Density Functional Theory for the Calculation of Sulfur K-Edge X-ray Absorption Spectra DeBeer George, Serena; Neese, Frank Inorganic Chemistry, Vol. 49, Issue 4 https://doi.org/10.1021/ic902202s	journal	February 2010
Solution NMR Structure of a Designed Metalloprotein and Complementary Molecular Dynamics Refinement Calhoun, Jennifer R.; Liu, Weixia; Spiegel, Katrin Structure, Vol. 16, Issue 2 https://doi.org/10.1016/j.str.2007.11.011	journal	February 2008
Redox Non-Innocent Ligands: Versatile New Tools to Control Catalytic Reactions Lyaskovskyy, Volodymyr; de Bruin, Bas ACS Catalysis, Vol. 2, Issue 2 https://doi.org/10.1021/cs200660v	journal	January 2012
Bimetallic Complexes Supported by a Redox-Active Ligand with Fused Pincer-Type Coordination Sites Wang, Denan; Lindeman, Sergey V.; Fiedler, Adam T. Inorganic Chemistry, Vol. 54, Issue 17 https://doi.org/10.1021/acs.inorgchem.5b01380	journal	August 2015
Abnormal NHC Palladium Complexes: Synthesis, Structure, and Reactivity Poulain, Aurelie; Iglesias, Manuel; Albrecht, Martin Current Organic Chemistry, Vol. 15, Issue 18 https://doi.org/10.2174/138527211797248049	journal	September 2011
Progression of Diiminopyridines: From Single Application to Catalytic Versatility Flisak, Zygmunt; Sun, Wen-Hua ACS Catalysis, Vol. 5, Issue 8 https://doi.org/10.1021/acscatal.5b00820	journal	July 2015
O ₂ Activation and Catalytic Alcohol Oxidation by Re Complexes with Redox-Active Ligands: A DFT Study of Mechanism Dinda, Shrabani; Genest, Alexander; Rösch, Notker ACS Catalysis, Vol. 5, Issue 8 https://doi.org/10.1021/acscatal.5b00509	journal	July 2015
Noninnocence in Metal Complexes: A Dithiolene Dawn Eisenberg, Richard; Gray, Harry B. Inorganic Chemistry, Vol. 50, Issue 20 https://doi.org/10.1021/ic2011748	journal	October 2011
Experimental and Computational Investigation of Thiolate Alkylation in Ni ^II and Zn ^II Complexes: Role of the Metal on the Sulfur Nucleophilicity Gennari, Marcello; Retegan, Marius; DeBeer, Serena Inorganic Chemistry, Vol. 50, Issue 20 https://doi.org/10.1021/ic200899w	journal	October 2011
How Innocent are Potentially Redox Non-Innocent Ligands? Electronic Structure and Metal Oxidation States in Iron-PNN Complexes as a Representative Case Study Butschke, Burkhard; Fillman, Kathlyn L.; Bendikov, Tatyana Inorganic Chemistry, Vol. 54, Issue 10 https://doi.org/10.1021/acs.inorgchem.5b00509	journal	April 2015
Kβ Mainline X-ray Emission Spectroscopy as an Experimental Probe of Metal–Ligand Covalency Pollock, Christopher J.; Delgado-Jaime, Mario Ulises; Atanasov, Mihail Journal of the American Chemical Society, Vol. 136, Issue 26 https://doi.org/10.1021/ja504182n	journal	June 2014
Using solution- and solid-state S K-edge X-ray absorption spectroscopy with density functional theory to evaluate M–S bonding for MS ₄ ²⁻ (M = Cr, Mo, W) dianions Olson, Angela C.; Keith, Jason M.; Batista, Enrique R. Dalton Trans., Vol. 43, Issue 46 https://doi.org/10.1039/C4DT02302A	journal	January 2014
Polarized-Neutron Study of the Magnetic Moment Density in Antiferromagnetic CuS $O_{4}$ Menzinger, F.; Cox, D. E.; Frazer, B. C. Physical Review, Vol. 181, Issue 2 https://doi.org/10.1103/PhysRev.181.936	journal	May 1969
High Covalence in CuSO ₄ and the Radicalization of Sulfate: An X-ray Absorption and Density Functional Study Szilagyi, Robert K.; Frank, Patrick; DeBeer George, Serena Inorganic Chemistry, Vol. 43, Issue 26 https://doi.org/10.1021/ic030311l	journal	December 2004
Synthesis and x-ray crystal structure of 2,2′,2″-iminotris(acetamidoxime) copper(II) sulphate monohydrate, [CuN(CH2CNH2: NOH)3(SO4)]·H2O Pearse, George A.; Raithby, Paul R.; Maughan, Maria M. J. Polyhedron, Vol. 13, Issue 4 https://doi.org/10.1016/S0277-5387(00)84731-2	journal	January 1994
Five-Coordinated High-Spin Complexes of Bivalent Cobalt, Nickel, andCopper with Tris(2-dimethylaminoethyl)amine Ciampolini, M.; Nardi, N. Inorganic Chemistry, Vol. 5, Issue 1 https://doi.org/10.1021/ic50035a010	journal	January 1966
1:1 Metal Complexes of Bivalent Cobalt, Nickel, Copper, Zink, and Cadmium with the Tripodal Ligand tris[2-(dimethylamino)ethyl]amine: Their stabilities and the X-ray crystal structure of its copper(II) complex sulfate Anderegg, Giorgio; Gramlich, Volker Helvetica Chimica Acta, Vol. 77, Issue 3 https://doi.org/10.1002/hlca.19940770312	journal	May 1994
Vanadium complexes as models for vanadium species of marine organisms. Synthesis, X-ray structure of oxo(O,O-sulfate)(2,2′:6′,2″-terpyridine)vanadium(IV) hydrate, and density functional geometry optimization analysis of vanadyl complexes Pifferi, Claudia; Picchi, Maria Pia; Cini, Renzo Polyhedron, Vol. 19, Issue 1 https://doi.org/10.1016/S0277-5387(99)00325-3	journal	January 2000
Mössbauer and thermogravimetric analysis of the oxidation pathway in the thermal decomposition of FeSO4·7H2O Bristoti, A.; Kunrath, J. I.; Viccaro, P. J. Journal of Inorganic and Nuclear Chemistry, Vol. 37, Issue 5 https://doi.org/10.1016/0022-1902(75)80460-X	journal	May 1975
A novel thermogravimetric analyser Mahgerefteh, H.; Khoory, H.; Khodaverdian, A. Thermochimica Acta, Vol. 237, Issue 1 https://doi.org/10.1016/0040-6031(94)85197-2	journal	April 1994
Thermogravimetric analysis of hexa- and heptahydrate crystals and packed powder of nickel sulfate Nandi, P. N.; Deshpande, D. A.; Kher, V. G. Thermochimica Acta, Vol. 32, Issue 1-2 https://doi.org/10.1016/0040-6031(79)85102-3	journal	September 1979
Thermogravimetric analysis of cobalt sulfate Nandi, P. N.; Kher, V. G.; Wankar, G. B. Thermochimica Acta, Vol. 41, Issue 2 https://doi.org/10.1016/0040-6031(80)80069-4	journal	November 1980
The dehydration of ZnSO4·7H2O and NiSO4·6H2O Rabbering, G.; Wanrooy, J.; Schuijff, A. Thermochimica Acta, Vol. 12, Issue 1 https://doi.org/10.1016/0040-6031(75)85008-8	journal	May 1975
Study of The Mechanism and Kinetic Parameters of The Thermal Decomposition of Cobalt Sulphate Hexahydrate Straszko, J.; Olszak-Humienik, M.; Możejko, J. Journal of Thermal Analysis and Calorimetry, Vol. 59, Issue 3, p. 935-942 https://doi.org/10.1023/A:1010186628054	journal	January 2000
[16] SHELXL: High-resolution refinement Sheldrick, George M.; Schneider, Thomas R. Methods in Enzymology https://doi.org/10.1016/S0076-6879(97)77018-6	book	January 1997
Sulfur K-edge X-ray absorption studies using the 54-pole wiggler at SSRL in undulator mode Hedman, Britt; Frank, Patrick; Penner-Hahn, James E. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 246, Issue 1-3 https://doi.org/10.1016/0168-9002(86)90196-8	journal	May 1986
Sulfur K-Edge X-ray Absorption Spectroscopy of 2Fe−2S Ferredoxin: Covalency of the Oxidized and Reduced 2Fe Forms and Comparison to Model Complexes Anxolabéhère-Mallart, Elodie; Glaser, Thorsten; Frank, Patrick Journal of the American Chemical Society, Vol. 123, Issue 23 https://doi.org/10.1021/ja010472t	journal	June 2001
Geometrical fitting of experimental XANES spectra by a full multiple-scattering procedure Benfatto, M.; Della Longa, S. Journal of Synchrotron Radiation, Vol. 8, Issue 4 https://doi.org/10.1107/S0909049501006422	journal	June 2001
Natural widths of atomic K and L levels, K α X‐ray lines and several K L L Auger lines Krause, M. O.; Oliver, J. H. Journal of Physical and Chemical Reference Data, Vol. 8, Issue 2 https://doi.org/10.1063/1.555595	journal	April 1979
Transferability of natural bond orbitals Carpenter, J. E.; Weinhold, Frank. Journal of the American Chemical Society, Vol. 110, Issue 2 https://doi.org/10.1021/ja00210a008	journal	January 1988
Natural hybrid orbitals Foster, J. P.; Weinhold, F. Journal of the American Chemical Society, Vol. 102, Issue 24 https://doi.org/10.1021/ja00544a007	journal	September 1980
Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint Reed, Alan E.; Curtiss, Larry A.; Weinhold, Frank Chemical Reviews, Vol. 88, Issue 6 https://doi.org/10.1021/cr00088a005	journal	September 1988
Molecular excitation energies to high-lying bound states from time-dependent density-functional response theory: Characterization and correction of the time-dependent local density approximation ionization threshold Casida, Mark E.; Jamorski, Christine; Casida, Kim C. The Journal of Chemical Physics, Vol. 108, Issue 11 https://doi.org/10.1063/1.475855	journal	March 1998
Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation Perdew, John P.; Chevary, J. A.; Vosko, S. H. Physical Review B, Vol. 46, Issue 11 https://doi.org/10.1103/PhysRevB.46.6671	journal	September 1992
Electronic structure of [Ni(II)S4] complexes from S K-edge X-ray absorption spectroscopy Queen, Matt S.; Towey, Bradley D.; Murray, Kevin A. Coordination Chemistry Reviews, Vol. 257, Issue 2 https://doi.org/10.1016/j.ccr.2012.07.020	journal	January 2013
Electronic structure and its relation to function in copper proteins Szilagyi, Robert K.; Solomon, Edward I. Current Opinion in Chemical Biology, Vol. 6, Issue 2 https://doi.org/10.1016/S1367-5931(02)00304-6	journal	April 2002
Fully optimized contracted Gaussian basis sets of triple zeta valence quality for atoms Li to Kr Schäfer, Ansgar; Huber, Christian; Ahlrichs, Reinhart The Journal of Chemical Physics, Vol. 100, Issue 8 https://doi.org/10.1063/1.467146	journal	April 1994
Iron–sulfur bond covalency from electronic structure calculations for classical iron–sulfur clusters Harris, Travis V.; Szilagyi, Robert K. Journal of Computational Chemistry, Vol. 35, Issue 7 https://doi.org/10.1002/jcc.23518	journal	January 2014
Electronic Population Analysis on LCAO–MO Molecular Wave Functions. I Mulliken, R. S. The Journal of Chemical Physics, Vol. 23, Issue 10 https://doi.org/10.1063/1.1740588	journal	October 1955
A quantum theory of molecular structure and its applications Bader, Richard F. W. Chemical Reviews, Vol. 91, Issue 5 https://doi.org/10.1021/cr00005a013	journal	July 1991
Higher Derivative Analysis of Complex Absorption Spectra Butler, W. L.; Hopkins, D. W. Photochemistry and Photobiology, Vol. 12, Issue 6 https://doi.org/10.1111/j.1751-1097.1970.tb06076.x	journal	December 1970
Resolution of overlapping UV–Vis absorption bands and quantitative analysis Antonov, Liudmil; Nedeltcheva, Daniela Chemical Society Reviews, Vol. 29, Issue 3 https://doi.org/10.1039/a900007k	journal	January 2000
X-ray absorption spectroscopic studies of the blue copper site: metal and ligand K-edge studies to probe the origin of the EPR hyperfine splitting in plastocyanin Shadle, Susan E.; Penner-Hahn, James E.; Schugar, Harvey J. Journal of the American Chemical Society, Vol. 115, Issue 2 https://doi.org/10.1021/ja00055a057	journal	January 1993
Spectroscopic and DFT Investigation of [M{HB(3,5- ⁱ ^{Pr ₂ pz) ₃ }(SC ₆ F ₅ )] (M = Mn, Fe, Co, Ni, Cu, and Zn) Model Complexes: Periodic Trends in Metal−Thiolate Bonding} Gorelsky, Serge I.; Basumallick, Lipika; Vura-Weis, Josh Inorganic Chemistry, Vol. 44, Issue 14 https://doi.org/10.1021/ic050371m	journal	July 2005
Ligand K-edge X-ray absorption spectroscopic studies: metal-ligand covalency in transition metal tetrathiolates Rose Williams, Kendra; Hedman, Britt; Hodgson, Keith O. Inorganica Chimica Acta, Vol. 263, Issue 1-2 https://doi.org/10.1016/S0020-1693(97)05663-6	journal	October 1997
Absolute electronegativity and hardness: application to inorganic chemistry Pearson, Ralph G. Inorganic Chemistry, Vol. 27, Issue 4 https://doi.org/10.1021/ic00277a030	journal	February 1988
Looking for jarosite on Mars: The low-temperature crystal structure of jarosite Mills, S. J.; Nestola, F.; Kahlenberg, V. American Mineralogist, Vol. 98, Issue 11-12 https://doi.org/10.2138/am.2013.4587	journal	November 2013
Preparation and Structures of K ₃ [V ^III (ox) ₂ ( μ -SO ₄ )] and K ₅ [V ^III (ox) ₂ (SO ₄ ) ₂ ] Kanamori, Kan; Kunita, Noriko; Okamoto, Ken-ichi Bulletin of the Chemical Society of Japan, Vol. 66, Issue 9 https://doi.org/10.1246/bcsj.66.2574	journal	September 1993
Investigation of the Electronic Structure of 2Fe−2S Model Complexes and the Rieske Protein Using Ligand K-Edge X-ray Absorption Spectroscopy Rose, Kendra; Shadle, Susan E.; Glaser, Thorsten Journal of the American Chemical Society, Vol. 121, Issue 11 https://doi.org/10.1021/ja983455l	journal	March 1999
Covalent Bonding: The Role of Exchange Effects Mayer, I. The Journal of Physical Chemistry A, Vol. 118, Issue 13 https://doi.org/10.1021/jp501232u	journal	March 2014
A predictive theoretical model for electron tunneling pathways in proteins Onuchic, José Nelson; Beratan, David N. The Journal of Chemical Physics, Vol. 92, Issue 1 https://doi.org/10.1063/1.458426	journal	January 1990
Long-Range Electron Tunneling Winkler, Jay R.; Gray, Harry B. Journal of the American Chemical Society, Vol. 136, Issue 8 https://doi.org/10.1021/ja500215j	journal	February 2014
Direct evaluation of electronic coupling mediated by hydrogen bonds: implications for biological electron transfer de Rege, P.; Williams, S.; Therien, M. Science, Vol. 269, Issue 5229 https://doi.org/10.1126/science.7660123	journal	September 1995
DFT-based Green's function pathways model for prediction of bridge-mediated electronic coupling Berstis, Laura; Baldridge, Kim K. Physical Chemistry Chemical Physics, Vol. 17, Issue 46 https://doi.org/10.1039/C5CP01861G	journal	January 2015
Electron tunneling in azurin: the coupling across a β-sheet Regan, J. J.; Di Bilio, A. J.; Langen, R. Chemistry & Biology, Vol. 2, Issue 7 https://doi.org/10.1016/1074-5521(95)90266-X	journal	July 1995
Electron tunneling through covalent and noncovalent pathways in proteins Beratan, David N.; Onuchic, José Nelson; Hopfield, J. J. The Journal of Chemical Physics, Vol. 86, Issue 8 https://doi.org/10.1063/1.452723	journal	April 1987
Electron tunneling pathways in ruthenated proteins Beratan, David N.; Onuchic, Jose Nelson; Betts, Jonathan N. Journal of the American Chemical Society, Vol. 112, Issue 22 https://doi.org/10.1021/ja00178a011	journal	October 1990
Electron transfer in ruthenium-modified proteins Winkler, Jay R.; Gray, Harry B. Chemical Reviews, Vol. 92, Issue 3 https://doi.org/10.1021/cr00011a001	journal	May 1992
Electron Flow through Metalloproteins Winkler, Jay R.; Gray, Harry B. Chemical Reviews, Vol. 114, Issue 7 https://doi.org/10.1021/cr4004715	journal	November 2013
Bonded-atom fragments for describing molecular charge densities Hirshfeld, F. L. Theoretica Chimica Acta, Vol. 44, Issue 2 https://doi.org/10.1007/bf00549096	journal	January 1977
Metalloprotein and redox protein design Kennedy, M. Current Opinion in Structural Biology, Vol. 11, Issue 4 https://doi.org/10.1016/s0959-440x(00)00237-2	journal	August 2001

Linked Research (4)

Similar Records

Trends in Covalency for d- and f-Element Metallocene Dichlorides Identified Using Chlorine K-Edge X-Ray Absorption Spectroscopy and Time Dependent-Density Functional Theory

Journal Article · Wed Sep 02 00:00:00 EDT 2009 · Journal of the American Chemical Society, 131(34):12125-12136 · OSTI ID:1353168

Kozimor, Stosh A; Yang, Ping; Batista, Enrique R; +7 more

Tetrahalide Complexes of the [U(NR)(2)]2+ Ion: Synthesis, Theory, and Chlorine K-Edge X-ray Absorption Spectroscopy

Journal Article · Wed Feb 13 00:00:00 EST 2013 · Journal of the American Chemical Society, 135(6):2279-2290 · OSTI ID:1353168

Spencer, Liam P.; Yang, Ping; Minasian, Stefan G.; +14 more

Determining Relative f and d Orbital Contributions to M–Cl Covalency in MCl ₆ ^2– (M = Ti, Zr, Hf, U) and UOCl ₅ ^– Using Cl K-Edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory

Journal Article · Wed Mar 28 00:00:00 EDT 2012 · Journal of the American Chemical Society · OSTI ID:1353168

Minasian, Stefan G.; Keith, Jason M.; Batista, Enrique R.; +11 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

CCDC 1497602: Experimental Crystal Structure Determination: TAVDIG : (2,2',2''-nitrilotris(N'-hydroxyethanimidamide))-(sulfato)-cobalt monohydrate Frank, Patrick; Szilágyi, Róbert; Gramlich, Volker https://doi.org/10.5517/ccdc.csd.cc1m8cr0 The current record is supplemented by this dataset	dataset	August 2016
CCDC 1497603: Experimental Crystal Structure Determination: TAVDOM : aqua-(2,2',2''-(nitrilo)tris(N'-hydroxyethanimidamide))-sulfato-nickel trihydrate Frank, Patrick; Szilágyi, Róbert; Gramlich, Volker https://doi.org/10.5517/ccdc.csd.cc1m8cs1 The current record is supplemented by this dataset	dataset	August 2016
CCDC 1497604: Experimental Crystal Structure Determination: TAVDUS : (2,2',2''-nitrilotris(N'-hydroxyethanimidamide))-sulfato-zinc(ii) monohydrate Frank, Patrick; Szilágyi, Róbert; Gramlich, Volker https://doi.org/10.5517/ccdc.csd.cc1m8ct2 The current record is supplemented by this dataset	dataset	August 2016
CCDC 1497605: Experimental Crystal Structure Determination: TAVFAA : (N,N-bis(2-(dimethylamino)ethyl)-N',N'-dimethylethane-1,2-diamine)-sulfato-copper(ii) trihydrate Frank, Patrick; Szilagyi, Robert K.; Gramlich, Volker https://doi.org/10.5517/ccdc.csd.cc1m8cv3 The current record is supplemented by this dataset	dataset	August 2016

Title: Spin-Polarization-Induced Preedge Transitions in the Sulfur K-Edge XAS Spectra of Open-Shell Transition-Metal Sulfates: Spectroscopic Validation of σ-Bond Electron Transfer

Citation Formats

References (66)

Linked Research (4)

Similar Records

Related Subjects