Assignment of pre‐edge peaks in K‐edge x‐ray absorption spectra of 3d transition metal compounds: electric dipole or quadrupole?

The characteristics of pre-edge peaks in K-edge x-ray absorption near edge structure (XANES) spectra of 3d transition metals were reviewed from viewpoints of the selection rule, coordination number, number of d-electrons, and symmetry of the coordination sphere. The contribution of the electric dipole and quadrupole transition to the peaks was discussed on the basis of the group theory, polarized spectra, and theoretical calculations. The pre-edge peak intensity for Td symmetry is larger than those for Oh symmetry for all 3d elements. The intense pre-edge peak for tetrahedral species of 3d transition metals is not due to 1s–3d transition, but transition to the p component in d–p hybridized orbital. The mixing of metal 4p orbitals with the 3d orbitals depends strongly on the coordination symmetry, and the possibility is predictable by group theory. The transition of 1s electron to d orbitals is electric quadrupole component in any of the symmetries. The d–p hybridization does not occur with regular octahedral symmetry, and the weak pre-edge peak consists of 1s–3d electric quadrupole transition. The pre-edge peak intensity for a compound with a tetrahedral center changes as a function of the number of 3d electrons regardless of the kind of element; it is maximized at d0 and gradually decreases to zero at d10. The features of pre-edge peaks in K-edge XANES spectra for 4d elements and the L1-edge for 5d elements are analogous with those for 3d elements, but the pre-edge peak is broadened due to the wide natural width of the core level. Copyright © 2008 John Wiley & Sons, Ltd.

[1]  Tsunehiro Tanaka,et al.  Structural analysis of tungsten–zirconium oxide catalyst by W K‐edge and L1‐edge XAFS , 2008 .

[2]  Y. Hitomi,et al.  XAFS Study of Tungsten L1- and L3-Edges: Structural Analysis of WO3 Species Loaded on TiO2 as a Catalyst for Photo-oxidation of NH3 , 2008 .

[3]  P. T. Fonseca,et al.  Cluster model and band structure calculations ofV2O5: ReducedV5+symmetry and many-body effects , 2008 .

[4]  John C. H. Spence,et al.  Determination of Ti coordination from pre-edge peaks in Ti K-edge XANES , 2007 .

[5]  I. Persson,et al.  The hydration of the scandium(III) ion in aqueous solution and crystalline hydrates studied by XAFS spectroscopy, large-angle X-ray scattering and crystallography. , 2006, Dalton transactions.

[6]  Uwe Bergmann,et al.  1s2p resonant inelastic X-ray scattering of iron oxides. , 2005, The journal of physical chemistry. B.

[7]  Patricia Ann Mabrouk,et al.  Multi-spectroscopic study of Fe(II) in silicate glasses: Implications for the coordination environment of Fe(II) in silicate melts , 2005 .

[8]  A. Barbier,et al.  Hard X-ray resonant electronic spectroscopy in transition metal oxides , 2005 .

[9]  P. Mantica,et al.  β-decay studies of neutron-rich nuclei , 2005 .

[10]  F. Farges.  Ab initio and experimental pre-edge investigations of the Mn K-edge XANES in oxide-type materials , 2005 .

[11]  E. Solomon,et al.  Metal and ligand K-edge XAS of organotitanium complexes: metal 4p and 3d contributions to pre-edge intensity and their contributions to bonding. , 2005, Journal of the American Chemical Society.

[12]  S. Ikeda,et al.  XAFS study of local structure change in perovskite titanates , 2005 .

[13]  A. Marcelli,et al.  Quadrupolar transitions and medium-range-order effects in metal K-edge x-ray absorption spectra of 3d transition-metal compounds , 2004 .

[14]  T. Uozumi,et al.  Theory of KL23L23 Auger spectra around Ti-K pre-peaks of TiO2 , 2004 .

[15]  J. Hormes,et al.  The influence of coordination geometry and valency on the K-edge absorption near edge spectra of selected chromium compounds , 2004 .

[16]  Eric L. Shirley,et al.  Ti 1s pre-edge features in rutile: a Bethe-Salpeter calculation , 2004 .

[17]  Qinghong Zhang,et al.  Characterizations and catalytic properties of Cr-MCM-41 prepared by direct hydrothermal synthesis and template-ion exchange , 2003 .

[18]  A. Ankudinov,et al.  Calculation and interpretation of K-shell x-ray absorption near-edge structure of transition metal oxides , 2003 .

[19]  M. Fernández-García.  XANES analysis of catalytic systems under reaction conditions , 2002 .

[20]  C. Lamberti,et al.  Evolution of Extraframework Iron Species in Fe Silicalite: 1. Effect of Fe Content, Activation Temperature, and Interaction with Redox Agents , 2002 .

[21]  Tsunehiro Tanaka,et al.  Local Structure of Framework Iron in Fe-Substituted Al-Mordenites by Fe K Edge XAFS , 2002 .

[22]  Tsunehiro Tanaka,et al.  NO Reduction with CO in the Presence of O2 over Cu/Al2O3 (3) – Structural Analysis of Active Species by Means of XAFS and UV/VIS/NIR Spectroscopy , 2002 .

[23]  A. Novakovich,et al.  Experimental and Theoretical Studies of Fine Structure in Polarized Ni K X-Ray Absorption Spectra of NiO Single Crystals , 2001 .

[24]  P. Petit,et al.  Transition elements in water-bearing silicate glasses/melts. part I. a high-resolution and anharmonic analysis of Ni coordination environments in crystals, glasses, and melts , 2001 .

[25]  S. Imamura,et al.  The Structure of Zirconium Oxide in Silica Matrix and its Epoxidation Activity , 2001 .

[26]  C. Brouder,et al.  Calculation of multipole transitions at the Fe K pre-edge through p-d hybridization in the Ligand Field Multiplet model , 2000 .

[27]  O. Šipr,et al.  Geometric and electronic structure effects in polarized V K-edge absorption near-edge structure spectra of V 2 O 5 , 1999 .

[28]  T. Hatsui,et al.  Strong metal-to-ligand charge transfer bands observed in Ni K- and L-edge XANES of planar Ni complexes. , 1999, Journal of synchrotron radiation.

[29]  H. Renevier,et al.  ELECTRON POPULATION ANALYSIS BY FULL-POTENTIAL X-RAY ABSORPTION SIMULATIONS , 1999 .

[30]  Tsunehiro Tanaka,et al.  STRUCTURAL ANALYSIS OF IRON AND MANGANESE SPECIES IN IRON- AND MANGANESE-PROMOTED SULFATED ZIRCONIA , 1999 .

[31]  Tsunehiro Tanaka,et al.  Structure of surface tantalate species and photo-oxidation of carbon monoxide over silica-supported tantalum oxide , 1999 .

[32]  B. Poumellec,et al.  Experimental and theoretical studies of dipole and quadrupole contributions to the vanadium K -edge XANES for VOPO 4 ⋅ 2 H 2 O xerogel , 1998 .

[33]  V. Eyert,et al.  Electronic structure of V 2 O 5 : Role of octahedral deformations , 1998 .

[34]  J. Hanson,et al.  Electronic Properties and Phase Transformations in CoMoO4 and NiMoO4: XANES and Time-Resolved Synchrotron XRD Studies , 1998 .

[35]  G. A. Parks,et al.  Differential redox and sorption of Cr (III/VI) on natural silicate and oxide minerals: EXAFS and XANES results , 1997 .

[36]  J. Rehr,et al.  TI K-EDGE XANES STUDIES OF TI COORDINATION AND DISORDER IN OXIDE COMPOUNDS: COMPARISON BETWEEN THEORY AND EXPERIMENT , 1997 .

[37]  K. Hodgson,et al.  A Multiplet Analysis of Fe K-Edge 1s → 3d Pre-Edge Features of Iron Complexes , 1997 .

[38]  Gordon E. Brown,et al.  Coordination chemistry of Ti(IV) in silicate glasses and melts: I. XAFS study of titanium coordination in oxide model compounds , 1996 .

[39]  M. Fröba,et al.  XANES studies on rhenium L absorption edges of Re2O7 graphite intercalation compounds and of other rhenium-oxygen compounds , 1996 .

[40]  Tsunehiro Tanaka,et al.  Structure of Mo−Mg Binary Oxides in Oxidized/Reduced States Studied by X-ray Absorption Spectroscopy at the Mo K Edge and Mg K Edge , 1996 .

[41]  C. Lamberti,et al.  Structure and reactivity of framework and extraframework iron in Fe-silicalite as investigated by spectroscopic and physicochemical methods , 1996 .

[42]  M. Shirai,et al.  In situ polarized total-reflection fluorescence X-ray absorption near-edge structure spectroscopy for the analysis of oriented structure of vanadium oxides on ZrO2(100) , 1994 .

[43]  Hideki Yamamoto,et al.  X-ray absorption fine structure (XAFS) study on the coordination of Te in PbOTiO2TeO2 glasses with high third-order optical non-linearity , 1994 .

[44]  C. Lamberti,et al.  XAFS Study of Ti-Silicalite - Structure of Framework Ti(IV) in the Presence and Absence of Reactive Molecules (H2O, NH3) and Comparison with Ultraviolet-Visible and Ir Results , 1994 .

[45]  Chen,et al.  X-ray-absorption studies of zirconia polymorphs. I. Characteristic local structures. , 1993, Physical review. B, Condensed matter.

[46]  B. Poumellec,et al.  Polarized xanes and exafs at the V K-edge of VOPO4 · 2H2O gel, comparison with the V K-edge in V2O5 xerogel , 1993 .

[47]  H. Nakamatsu,et al.  DV-Xα Molecular Orbital Method for X-ray Absorption Near Edge Structure–Application to N2 and CrO42- , 1993 .

[48]  Satohiro Yoshida,et al.  Analysis of XANES for identification of highly dispersed transition metal oxides on supports , 1992 .

[49]  E. Beaurepaire,et al.  Experimental and Theoretical Investigation of the Pre-Peaks at the Ti K-Edge Absorption Spectra in TiO2 , 1992 .

[50]  M. Sano,et al.  XANES spectra of copper(II) complexes: correlation of the intensity of the 1s .fwdarw. 3d transition and the shape of the complex , 1992 .

[51]  M. Ruiz‐López,et al.  A theoretical study of the XANES spectra of rutile and anatase , 1991 .

[52]  G. Guo,et al.  Electronic structure and X-ray absorption spectrum of rutile TiO2 , 1991 .

[53]  M. Kunz,et al.  Fe, Ti ordering and octahedral distortions in acentric neptunite: Temperature dependent X-ray and neutron structure refinements and Mössbauer spectroscopy , 1991 .

[54]  C. Brouder.  Angular dependence of X-ray absorption spectra , 1990 .

[55]  García,et al.  Structure of oriented V2O5 gel studied by polarized x-ray-absorption spectroscopy at the vanadium K edge. , 1989, Physical Review B (Condensed Matter).

[56]  N. Kosugi,et al.  Electron energy loss and X-ray absorption spectroscopy of rutile and anatase: a test of structural sensitivity , 1989 .

[57]  Marucco,et al.  X-ray-absorption near-edge structure of titanium and vanadium in (Ti,V)O2 rutile solid solutions. , 1987, Physical review. B, Condensed matter.

[58]  T. Yokoyama,et al.  Polarization dependence of XANES of square-planar Ni(CN)2−4 ion. A comparison with octahedral Fe(CN)4−6 and Fe(CN)3−6 ions , 1986 .

[59]  T. Yokoyama,et al.  Polarized xanes spectra of CuCl2 · 2H2O. Further evidence for shake-down phenomena , 1986 .

[60]  B. Poumellec,et al.  X‐ray absorption K‐edge spectra of titanium in (Ti, Nb)O2 rutile solid solutions , 1986 .

[61]  J. Bart.  Near-Edge X-Ray Absorption Spectroscopy in Catalysis , 1986 .

[62]  D. H. Maylotte,et al.  A Study of the K-edge Absorption Spectra of Selected Vanadium Compounds. , 1984 .

[63]  J. Widom,et al.  X-ray absorption spectroscopy of iron-tyrosinate proteins , 1984 .

[64]  L. A. Grunes.  Study of the K edges of 3 d transition metals in pure and oxide form by x-ray-absorption spectroscopy , 1983 .

[65]  Sebastian Doniach,et al.  Observation of an electric quadrupole transition in the X-ray absorption spectrum of a Cu(II) complex , 1982 .

[66]  W. Goddard,et al.  Ab initio studies of the x-ray absorption edge in copper complexes. I. Atomic Cu 2 + and Cu(ii) Cl 2 , 1980 .

[67]  K. Hodgson,et al.  Structural study of the vanadium complex in living ascidian blood cells by x-ray absorption spectroscopy , 1980 .

[68]  M. Krause,et al.  Natural widths of atomic K and L levels, Kα X‐ray lines and several KLL Auger lines , 1979 .

[69]  U. C. Srivastava,et al.  X-ray absorption edge spectrometry (xaes) as applied to coordination chemistry , 1973 .

[70]  G. Rossi,et al.  The crystal structure of neptunite , 1966 .

[71]  F. Cotton,et al.  Soft X‐Ray Absorption Edges of Metal Ions in Complexes. I. Theoretical Considerations , 1956 .

[72]  F. Cotton,et al.  Soft X‐Ray Absorption Edges of Metal Ions in Complexes. II. Cu K Edge in Some Cupric Complexes , 1956 .

[73]  W. W. Beeman,et al.  The Mn K Absorption Edge in Manganese Metal and Manganese Compounds , 1949 .

[74]  D. Coster.  Über die Absorptionsspektren im Röntgengebiet , 1924 .

[75]  H. Fricke.  The K-Characteristic Absorption Frequencies for the Chemical Elements Magnesium to Chromium , 1920 .