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X-ray emission spectroscopy

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Abstract

We describe the chemical information that can be obtained by means of hard X-ray emission spectroscopy (XES). XES is presented as a technique that is complementary to X-ray absorption spectroscopy (XAS) and that provides valuable information with respect to the electronic structure (local charge- and spin-density) as well as the ligand environment of a 3d transition metal. We address non-resonant and resonant XES and present results that were recorded on Mn model systems and the Mn4Ca-cluster in the oxygen evolving complex of photosystem II. A brief description of the instrumentation is given with an outlook toward future developments.

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References

  • Ascone I, Meyer-Klaucke W, Murphy L (2003) Experimental aspects of biological X-ray absorption spectroscopy. J Synchrotron Radiat 10:16–22

    Google Scholar 

  • Ballhausen CJ (1962) Introduction to ligand field theory. McGraw-Hill, New York

  • Bergmann U, Cramer SP (1998) SPIE—the international society for optical engineering. Society of Photo-Optical Instrumentation Engineers, San Diego, California, pp 198–209

    Google Scholar 

  • Bergmann U, Grush MM, Horne CR, De Marois P, PennerHahn JE, Yocum CF, Wright DW, Dube CE, Armstrong WH, Christou G, Eppley HJ, Cramer SP (1998) Characterization of the Mn oxidation states in photosystem II by Kß X-ray fluorescence spectroscopy. J Phys Chem B 102:8350–8352

    Article  CAS  Google Scholar 

  • Bergmann U, Glatzel P, de Groot F, Cramer SP (1999a) High resolution K capture X-ray fluorescence spectroscopy: a new tool for chemical characterization. J Am Chem Soc 121:4926–4927

    Article  CAS  Google Scholar 

  • Bergmann U, Horne CR, Collins TJ, Workman JM, Cramer SP (1999b) Chemical dependence of interatomic X-ray transition energies and intensities—a study of Mn Kß ‘‘and Kß(2, 5) spectra. Chem Phys Lett 302:119–124

    Article  CAS  Google Scholar 

  • Bergmann U, Glatzel P, Robblee JH, Messinger J, Fernandez C, Cinco R, Visser H, McFarlane K, Bellacchio E, Pizarro S, Sauer K, Yachandra VK, Klein MP, Cox BL, Nealson KH, Cramer SP (2001) High-resolution X-ray spectroscopy of rare events: a different look at local structure and chemistry. J Synchrotron Radiat 8:199–203

    Article  CAS  PubMed  Google Scholar 

  • Bergmann U, Bendix J, Glatzel P, Gray HB, Cramer SP (2002) Anisotropic valence → core x-ray fluorescence from a [Rh(en)3][Mn(N)(CN)5]center dot H2O single crystal: experimental results and density functional calculations. J Chem Phys 116:2011–2015

    Article  CAS  Google Scholar 

  • Bransden BH, Joachain CJ (1983) Physics of atoms and molecules. Longman Scientific & Technical, Essex

    Google Scholar 

  • Carra P, Fabrizio M, Thole BT (1995) High-resolution X-ray resonant Raman-scattering. Phys Rev Lett 74:3700–3703

    Google Scholar 

  • Cramer SP (1988) In: Konigsberger D, Prins R (eds) Extended X-ray absorption fine structure. Plenum, New York, pp 257–320

  • Cramer SP, de Groot FMF, Ma Y, Chen CT, Sette F, Kipke CA, Eichhorn DM, Chan MK, Armstrong WH, Libby E, Christou G, Brooker S, Mckee V, Mullins OC, Fuggle JC (1991) Ligand field strengths and oxidation states from manganese L-edge spectroscopy. J Am Chem Soc 113:7937–7940

    Article  CAS  Google Scholar 

  • de Groot FMF (1994) X-ray absorption and dichroism of transition metals and their compounds. J Electron Spectrosc 676:529–622

    Article  Google Scholar 

  • de Groot F (2005) Multiplet effects in X-ray spectroscopy. Coord Chem Rev 249:31–63

    Article  Google Scholar 

  • de Groot FMF, Kotani A (2008) Core level spectroscopy of solids. Taylor and Francis, New York

    Google Scholar 

  • de Groot FMF, Grioni M, Fuggle JC, Ghijsen J, Sawatzky GA, Petersen H (1989) Oxygen 1s X-ray-absorption edges of transition-metal oxides. Phys Rev B 40:5715–5723

    Article  Google Scholar 

  • de Groot FMF, Glatzel P, Bergmann U, van Aken PA, Barrea RA, Klemme S, Havecker M, Knop-Gericke A, Heijboer WM, Weckhuysen BM (2005) 1s2p resonant inelastic X-ray scattering of iron oxides. J Phys Chem B 109:20751–20762

    Article  PubMed  Google Scholar 

  • de Groot F, Vanko G, Glatzel P (2009) The 1s x-ray absorption pre-edge structures in transition metal oxides. J Phys Condens Matter 21:104207

    Article  Google Scholar 

  • Farges F (2005) Ab initio and experimental pre-edge investigations of the Mn K-edge XANES in oxide-type materials. Phys Rev B 71:155109

    Article  Google Scholar 

  • Figgis BN (1967) Introduction to ligand fields. Interscience, New York

  • Fuggle JC, Inglesfield JE (eds) (1992) Unoccupied electronic states. Springer-Verlag, Berlin

    Google Scholar 

  • Gamblin SD, Urch DS (2001) Metal K beta X-ray emission spectra of first row transition metal compounds. J Electron Spectrosc 113:179–192

    Article  CAS  Google Scholar 

  • Gel’mukhanov F, Agren H (1999) Resonant X-ray Raman scattering. Phys Rep Rev Sec Phys Lett 312:87–330

    Google Scholar 

  • Glatzel P (2001) X-ray fluorescence emission following K capture and 1s photoionization of Mn and Fe in various chemical environments, http://www.sub.uni-hamburg.de/opus/volltexte/2001/570/pdf/Disse.pdf, PhD Thesis, Hamburg University

  • Glatzel P, Bergmann U (2005) High resolution 1s core hole X-ray spectroscopy in 3d transition metal complexes—electronic and structural information. Coord Chem Rev 249:65–95

    Article  CAS  Google Scholar 

  • Glatzel P, Bergmann U, de Groot FMF, Cramer SP (2002) Multiple excitations in the K fluorescence emission of Mn, Fe and Ni compounds. In: Bianconi A, Marcelli A (eds) X-ray and inner-shell processes. American Institute of Physics, Rome, pp 250–253

    Google Scholar 

  • Glatzel P, Bergmann U, Yano J, Visser H, Robblee JH, Gu WW, de Groot FMF, Christou G, Pecoraro VL, Cramer SP, Yachandra VK (2004) The electronic structure of Mn in oxides, coordination complexes, and the oxygen-evolving complex of photosystem II studied by resonant inelastic X-ray scattering. J Am Chem Soc 126:9946–9959

    Article  CAS  PubMed  Google Scholar 

  • Glatzel P, Yano J, Bergmann U, Visser H, Robblee JH, Gu WW, de Groot FMF, Cramer SP, Yachandra VK (2005) Resonant inelastic X-ray scattering (RIXS) spectroscopy at the MnK absorption pre-edge—a direct probe of the 3d orbitals. J Phys Chem Solids 66:2163–2167

    Article  CAS  Google Scholar 

  • Glatzel P, Mirone A, Eeckhout SG, Sikora M, Giuli G (2008) Orbital hybridization and spin polarization in the resonant 1s photoexcitations of α-Fe2O3. Phys Rev B 77:115133

    Article  Google Scholar 

  • Glatzel P, Sikora M, Fernandez-Garcia M (2009) Resonant X-ray spectroscopy to study K absorption pre-edges in 3d transition metal compounds. Eur Phys J Spec Top 169:207–214

    Article  Google Scholar 

  • Goulon J, Goulon-Ginet C, Cortes R, Dubois JM (1982) On experimental attenuation factors of the amplitude of the EXAFS oscillations in absorption, reflectivity, and luminescence measurements. J Phys 43:539–548

    Google Scholar 

  • Hämäläinen K, Kao CC, Hastings JB, Siddons DP, Berman LE, Stojanoff V, Cramer SP (1992) Spin-dependent X-ray absorption of MnO and MnF2. Phys Rev B 46:14274–14277

    Article  Google Scholar 

  • Haumann M, Liebisch P, Muller C, Barra M, Grabolle M, Dau H (2005) Photosynthetic O-2 formation tracked by time-resolved X-ray experiments. Science 310:1019–1021

    Article  CAS  PubMed  Google Scholar 

  • Hayashi H, Kawata M, Takeda R, Udagawa Y, Watanabe Y, Takano T, Nanao S, Kawamura N (2004) A multi-crystal spectrometer with a two-dimensional position-sensitive detector and contour maps of resonant Kβ emission in Mn compounds. J Electron Spectrosc 136:191–197

    Article  CAS  Google Scholar 

  • Hayashi H, Sato A, Azumi T, Udagawa Y, Inami T, Ishii K, Garg KB (2006) Local spin ordering in the antiferromagnetic as well as paramagnetic LaMnO3 phase revealed by polarized spin-selected 1s → 3d absorption spectra. Phys Rev B 73:134405

    Article  Google Scholar 

  • Hill JP, Coburn DS, Kim YJ, Gog T, Casa DM, Kodituwakku CN, Sinn H (2007) A 2m inelastic X-ray scattering spectrometer at CMC-XOR, advanced photon source. J Synchrotron Radiat 14:361–365

    Article  CAS  PubMed  Google Scholar 

  • Hoszowska J, Dousse JC, Kern J, Rheme C (1996) High-resolution von Hamos crystal X-ray spectrometer. Nucl Instrum Methods A 376:129–138

    Article  CAS  Google Scholar 

  • Hudson AC, Stolte WC, Lindle DW, Guillemin R (2007) Design and performance of a curved-crystal x-ray emission spectrometer. Rev Sci Instrum 78:053101

    Article  CAS  PubMed  Google Scholar 

  • Huotari S, Vanko G, Albergamo F, Ponchut C, Graafsma H, Henriquet C, Verbeni R, Monaco G (2005) Improving the performance of high-resolution X-ray spectrometers with position-sensitive pixel detectors. J Synchrotron Radiat 12:467–472

    Article  CAS  PubMed  Google Scholar 

  • Izumi Y, Konishi K, Obaid DM, Miyajima T, Yoshitake H (2007) X-ray absorption fine structure combined with X-ray fluorescence spectroscopy. Monitoring of vanadium sites in mesoporous titania, excited under visible light by selective detection of vanadium Kß(5, 2) Fluorescence. Anal Chem 79:6933–6940

    Article  CAS  PubMed  Google Scholar 

  • Jaklevic J, Kirby JA, Klein MP, Robertson AS, Brown GS, Eisenberger P (1977) Fluorescence detection of EXAFS - sensitivity enhancement for dilute species and thin-films. Solid State Commun 23:679–682

    Google Scholar 

  • Kohn W, Sham LJ (1965) Self-consistent equations including exchange and correlation effects. Phys Rev 140:A1133

    Article  Google Scholar 

  • Kotani A, Shin S (2001) Resonant inelastic X-ray scattering spectra for electrons in solids. Rev Mod Phys 73:203–246

    Google Scholar 

  • Matta CF, Bader RFW (2006) An experimentalist’s reply to “What is an atom in a molecule?”. J Phys Chem A 110:6365–6371

    Article  CAS  PubMed  Google Scholar 

  • Meisel A, Leonhardt G, Szargan R (1989) X-ray spectra and chemical binding. Springer-Verlag, New York

    Google Scholar 

  • Messinger J, Robblee JH, Bergmann U, Fernandez C, Glatzel P, Visser H, Cinco RM, McFarlane KL, Bellacchio E, Pizarro SA, Cramer SP, Sauer K, Klein MP, Yachandra VK (2001) Absence of Mn-centered oxidation in the S(2) → S(3) transition: implications for the mechanism of photosynthetic water oxidation. J Am Chem Soc 123:7804–7820

    Article  CAS  PubMed  Google Scholar 

  • Mulliken RS (1955) Electronic population analysis on LCAO[Single Bond]MO molecular wave functions. J Chem Phys 23:1833

    Article  CAS  Google Scholar 

  • Peng G, de Groot FMF, Hämäläinen K, Moore JA, Wang X, Grush MM, Hastings JB, Siddons DP, Armstrong WH, Mullins OC, Cramer SP (1994) High-resolution manganese X-ray-fluorescence spectroscopy—oxidation-state and spin-state sensitivity. J Am Chem Soc 116:2914–2920

    Article  CAS  Google Scholar 

  • Penner-Hahn JE (2005) Characterization of “spectroscopically quiet” metals in biology. Coord Chem Rev 249:161–177

    Google Scholar 

  • Pizarro SA, Glatzel P, Visser H, Robblee JH, Christou G, Bergmann U, Yachandra VK (2004) Mn oxidation states in tri- and tetra-nuclear Mn compounds structurally relevant to photosystem II: Mn K-edge X-ray absorption and Kß X-ray emission spectroscopy studies. Phys Chem Chem Phys 6:4864–4870

    Google Scholar 

  • Safonov VA, Vykhodtseva LN, Polukarov YM, Safonova OV, Smolentsev G, Sikora M, Eeckhout SG, Glatzel P (2006) Valence-to-core X-ray emission spectroscopy identification of carbide compounds in nanocrystalline Cr coatings deposited from Cr(III) electrolytes containing organic substances. J Phys Chem B 110:23192–23196

    Article  CAS  PubMed  Google Scholar 

  • Sakurai K, Eba H (1999) X-ray fluorescence analysis with a Johansson-type spectrometer. Jpn J Appl Phys 1(38):650–653

    Google Scholar 

  • Schülke W (2007) Electron dynamics by inelastic X-ray scattering. Oxford University Press, Oxford

    Google Scholar 

  • Scott RA, Shokes JE, Cosper NJ, Jenney FE, Adams MWW (2005) Bottlenecks and roadblocks in high-throughput XAS for structural genomics. J Synchrotron Radiat 12:19–22

    Google Scholar 

  • Stojanoff V, Hämäläinen K, Siddons D, Hastings JB, Berman LE, Cramer S, Smith G (1992) A high-resolution x-ray fluorescence spectrometer for near-edge absorption studies. Rev Sci Instrum 63:1125–1127

    Article  CAS  Google Scholar 

  • Thole BT, van der Laan G (1988) Branching ratio in x-ray absorption spectroscopy. Phys Rev B 38:3158–3171

    Google Scholar 

  • Thole BT, Carra P, Sette F, van der Laan G (1992) X-ray circular dichroism as a probe of orbital magnetization. Phys Rev Lett 68:1943–1946

    Google Scholar 

  • Tsutsumi K (1959) The X-ray non-diagram lines Kß of some compounds of the iron group. Phys Soc Jpn 14:1696–1706

    Article  CAS  Google Scholar 

  • Tsutsumi K, Nakamori H, Ichikawa K (1976) X-ray Mn Kß emission spectra of manganese oxides and manganetes. Phys Rev B 13:929–933

    Article  CAS  Google Scholar 

  • Vankó G, Neisius T, Molnar G, Renz F, Karpati S, Shukla A, de Groot FMF (2006) Probing the 3d spin momentum with X-ray emission spectroscopy: the case of molecular-spin transitions. J Phys Chem B 110:11647–11653

    Article  PubMed  Google Scholar 

  • Visser H, Anxolabehere-Mallart E, Bergmann U, Glatzel P, Robblee JH, Cramer SP, Girerd JJ, Sauer K, Klein MP, Yachandra VK (2001) Mn K-edge XANES and Kß XES studies of two Mn-oxo binuclear complexes: investigation of three different oxidation states relevant to the oxygen-evolving complex of photosystem II. J Am Chem Soc 123:7031–7039

    Google Scholar 

  • Wang H, Ge P, Riordan CG, Brooker S, Woomer CG, Collins T, Melendres C, Graudejus O, Bartlett N, Cramer SP (1998) Counting holes in Ni complexes using integrated X-ray L absorption spectra. J Phys Chem B 102:8343–8346

    Google Scholar 

  • Weissbluth M (1978) Atoms and molecules. Plenum Press, New York

  • Welter E, Machek P, Dräger G, Bruggmann U, Froba M (2005) A new X-ray spectrometer with large focusing crystal analyzer. J Synchrotron Radiat 12:448–454

    Article  CAS  PubMed  Google Scholar 

  • Wiedemann H (2002) Synchrotron radiation. Springer, Berlin

    Google Scholar 

  • Yano J, Kern J, Irrgang K-D, Latimer MJ, Bergmann U, Glatzel P, Pushkar Y, Biesiadka J, Loll B, Sauer K, Messinger J, Zouni A, Yachandra VK (2005) X-ray damage to the Mn4Ca complex in single-crystals of photosystem II: a case study for metallo-protein crystallography, PNAS, 102, no. 34, 12047–12052

  • Yano J, Kern J, Sauer K, Latimer MJ, Pushkar Y, Biesiadka J, Loll B, Saenger W, Messinger J, Zouni A, Yachandra VK (2006) Where water is oxidized to dioxygen: structure of the photosynthetic Mn4Ca cluster. Science 314:821–825

    Article  CAS  PubMed  Google Scholar 

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Acknowledgments

Portions of this research were carried out at the Stanford Synchrotron Radiation Lightsource (SSRL), a national user facility operated by Stanford University on behalf of the U.S. Department of Energy, Office of Basic Energy Sciences. We acknowledge the European Synchrotron Radiation Facility and the staff of beamline ID26 and beamline ID16.

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  1. Stanford Synchrotron Radiation Lightsource, P.O. Box 20450, Stanford, CA, 94305, USA

    Uwe Bergmann

  2. European Synchrotron Radiation Facility (ESRF), BP22, 6 rue Jules Horowitz, 38043, Grenoble, France

    Pieter Glatzel

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  1. Uwe Bergmann
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  2. Pieter Glatzel
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Correspondence to Uwe Bergmann or Pieter Glatzel.

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Bergmann, U., Glatzel, P. X-ray emission spectroscopy. Photosynth Res 102, 255–266 (2009). https://doi.org/10.1007/s11120-009-9483-6

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