Photosynthesis Research

, 102:255 | Cite as

X-ray emission spectroscopy

Review

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.

Keywords

X-ray spectroscopy X-ray emission Synchrotron radiation Electronic structure Photosystem II Manganese Oxygen evolving complex 

References

  1. Ascone I, Meyer-Klaucke W, Murphy L (2003) Experimental aspects of biological X-ray absorption spectroscopy. J Synchrotron Radiat 10:16–22Google Scholar
  2. Ballhausen CJ (1962) Introduction to ligand field theory. McGraw-Hill, New YorkGoogle Scholar
  3. Bergmann U, Cramer SP (1998) SPIE—the international society for optical engineering. Society of Photo-Optical Instrumentation Engineers, San Diego, California, pp 198–209Google Scholar
  4. 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 102:8350–8352CrossRefGoogle Scholar
  5. 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 121:4926–4927CrossRefGoogle Scholar
  6. 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 302:119–124CrossRefGoogle Scholar
  7. 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 8:199–203CrossRefPubMedGoogle Scholar
  8. 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 116:2011–2015CrossRefGoogle Scholar
  9. Bransden BH, Joachain CJ (1983) Physics of atoms and molecules. Longman Scientific & Technical, EssexGoogle Scholar
  10. Carra P, Fabrizio M, Thole BT (1995) High-resolution X-ray resonant Raman-scattering. Phys Rev Lett 74:3700–3703 Google Scholar
  11. Cramer SP (1988) In: Konigsberger D, Prins R (eds) Extended X-ray absorption fine structure. Plenum, New York, pp 257–320Google Scholar
  12. 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 113:7937–7940CrossRefGoogle Scholar
  13. de Groot FMF (1994) X-ray absorption and dichroism of transition metals and their compounds. J Electron Spectrosc 676:529–622CrossRefGoogle Scholar
  14. de Groot F (2005) Multiplet effects in X-ray spectroscopy. Coord Chem Rev 249:31–63CrossRefGoogle Scholar
  15. de Groot FMF, Kotani A (2008) Core level spectroscopy of solids. Taylor and Francis, New YorkGoogle Scholar
  16. 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 40:5715–5723CrossRefGoogle Scholar
  17. 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 109:20751–20762CrossRefPubMedGoogle Scholar
  18. de Groot F, Vanko G, Glatzel P (2009) The 1s x-ray absorption pre-edge structures in transition metal oxides. J Phys Condens Matter 21:104207CrossRefGoogle Scholar
  19. Farges F (2005) Ab initio and experimental pre-edge investigations of the Mn K-edge XANES in oxide-type materials. Phys Rev B 71:155109CrossRefGoogle Scholar
  20. Figgis BN (1967) Introduction to ligand fields. Interscience, New York Google Scholar
  21. Fuggle JC, Inglesfield JE (eds) (1992) Unoccupied electronic states. Springer-Verlag, BerlinGoogle Scholar
  22. Gamblin SD, Urch DS (2001) Metal K beta X-ray emission spectra of first row transition metal compounds. J Electron Spectrosc 113:179–192CrossRefGoogle Scholar
  23. Gel’mukhanov F, Agren H (1999) Resonant X-ray Raman scattering. Phys Rep Rev Sec Phys Lett 312:87–330Google Scholar
  24. 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
  25. 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 249:65–95CrossRefGoogle Scholar
  26. 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 250–253Google Scholar
  27. 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 126:9946–9959CrossRefPubMedGoogle Scholar
  28. 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 66:2163–2167CrossRefGoogle Scholar
  29. 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 77:115133CrossRefGoogle Scholar
  30. 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 169:207–214CrossRefGoogle Scholar
  31. 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
  32. 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 46:14274–14277CrossRefGoogle Scholar
  33. 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 310:1019–1021CrossRefPubMedGoogle Scholar
  34. 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 136:191–197CrossRefGoogle Scholar
  35. 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 73:134405CrossRefGoogle Scholar
  36. 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 14:361–365CrossRefPubMedGoogle Scholar
  37. Hoszowska J, Dousse JC, Kern J, Rheme C (1996) High-resolution von Hamos crystal X-ray spectrometer. Nucl Instrum Methods A 376:129–138CrossRefGoogle Scholar
  38. Hudson AC, Stolte WC, Lindle DW, Guillemin R (2007) Design and performance of a curved-crystal x-ray emission spectrometer. Rev Sci Instrum 78:053101CrossRefPubMedGoogle Scholar
  39. 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 12:467–472CrossRefPubMedGoogle Scholar
  40. 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 79:6933–6940CrossRefPubMedGoogle Scholar
  41. 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 23:679–682Google Scholar
  42. Kohn W, Sham LJ (1965) Self-consistent equations including exchange and correlation effects. Phys Rev 140:A1133CrossRefGoogle Scholar
  43. Kotani A, Shin S (2001) Resonant inelastic X-ray scattering spectra for electrons in solids. Rev Mod Phys 73:203–246 Google Scholar
  44. Matta CF, Bader RFW (2006) An experimentalist’s reply to “What is an atom in a molecule?”. J Phys Chem A 110:6365–6371CrossRefPubMedGoogle Scholar
  45. Meisel A, Leonhardt G, Szargan R (1989) X-ray spectra and chemical binding. Springer-Verlag, New YorkGoogle Scholar
  46. 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 123:7804–7820CrossRefPubMedGoogle Scholar
  47. Mulliken RS (1955) Electronic population analysis on LCAO[Single Bond]MO molecular wave functions. J Chem Phys 23:1833CrossRefGoogle Scholar
  48. 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 116:2914–2920CrossRefGoogle Scholar
  49. Penner-Hahn JE (2005) Characterization of “spectroscopically quiet” metals in biology. Coord Chem Rev 249:161–177Google Scholar
  50. 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 6:4864–4870Google Scholar
  51. 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 110:23192–23196CrossRefPubMedGoogle Scholar
  52. Sakurai K, Eba H (1999) X-ray fluorescence analysis with a Johansson-type spectrometer. Jpn J Appl Phys 1(38):650–653Google Scholar
  53. Schülke W (2007) Electron dynamics by inelastic X-ray scattering. Oxford University Press, OxfordGoogle Scholar
  54. Scott RA, Shokes JE, Cosper NJ, Jenney FE, Adams MWW (2005) Bottlenecks and roadblocks in high-throughput XAS for structural genomics. J Synchrotron Radiat 12:19–22Google Scholar
  55. 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 63:1125–1127CrossRefGoogle Scholar
  56. Thole BT, van der Laan G (1988) Branching ratio in x-ray absorption spectroscopy. Phys Rev B 38:3158–3171Google Scholar
  57. Thole BT, Carra P, Sette F, van der Laan G (1992) X-ray circular dichroism as a probe of orbital magnetization. Phys Rev Lett 68:1943–1946Google Scholar
  58. Tsutsumi K (1959) The X-ray non-diagram lines Kß of some compounds of the iron group. Phys Soc Jpn 14:1696–1706CrossRefGoogle Scholar
  59. Tsutsumi K, Nakamori H, Ichikawa K (1976) X-ray Mn Kß emission spectra of manganese oxides and manganetes. Phys Rev B 13:929–933CrossRefGoogle Scholar
  60. 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 110:11647–11653CrossRefPubMedGoogle Scholar
  61. 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 123:7031–7039Google Scholar
  62. 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 102:8343–8346Google Scholar
  63. Weissbluth M (1978) Atoms and molecules. Plenum Press, New YorkGoogle Scholar
  64. Welter E, Machek P, Dräger G, Bruggmann U, Froba M (2005) A new X-ray spectrometer with large focusing crystal analyzer. J Synchrotron Radiat 12:448–454CrossRefPubMedGoogle Scholar
  65. Wiedemann H (2002) Synchrotron radiation. Springer, BerlinGoogle Scholar
  66. 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, 12047–12052Google Scholar
  67. 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 314:821–825CrossRefPubMedGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 2009

Authors and Affiliations

  1. 1.Stanford Synchrotron Radiation LightsourceStanfordUSA
  2. 2.European Synchrotron Radiation Facility (ESRF)GrenobleFrance

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