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Localization and hybridization of 5f states in the metallic and ionic bond as investigated by photoelectron spectroscopy

  • J. R. Naegele
  • J. Ghijsen
  • L. Manes
Conference paper
Part of the Structure and Bonding book series (STRUCTURE, volume 59/60)

Abstract

Localization versus itineracy and the degree of hybridization of 5 f states with orbitals of the actinide atom (especially 6 d) as well as with those of the ligand in compounds are central questions for the understanding of bonding in actinide solids. Photoelectron spectroscopy provides answers to these questions. In narrow band solids, like the actinides, the interpretation of results requires the use of band calculations in the itinerant picture, as well as models of final state emission in the atomic picture.

From the experimental viewpoint: l. the analysis of the variation of photoionization cross sections (affecting the intensities of photoelectron spectroscopy), gives an insight into the orbital composition of the bands of the solid; 2. the combination of direct and inverse photoemission provides a powerful tool to assess the structure of occupied and of empty states, and, in the case of localized 5 f states, permits the determination of a fundamental quantity, the Coulomb correlation energy, governing the physical properties of narrow bands.

After a survey of the basic theory and some experimental aspects of photoelectron spectroscopy which are relevant to actinide solids, two systems are illustrated: elemental actinide metals, in which the Mott transition between plutonium and americium is evidenced in a “photographic” way by photoemission, and strongly ionic oxides, in which the 5 f localized behaviour is clearly seen, and indications of f-p or d-p covalent mixing are investigated.

Keywords

Valence Band Core Level High Binding Energy Core Level Spectrum Empty State 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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References

  1. 1.
    Smith, J. L., Kmetko, E. A.: J. Less-Common Metals 90, 83 (1983)Google Scholar
  2. 2.
    Baptist, R.: Proceedings of the 12ème Journées des Actinides, Orsay (France) 1982Google Scholar
  3. 3.
    Baptist, R. et al.: J. Physique (Paris) 44, 241 (1983)Google Scholar
  4. 4.
    Fadley, C. S.: Basic Concepts of X-Ray Photoelectron Spectroscopy, in “Electron Spectroscopy: Theory, Techniques and Applications” (Brundle, C. R., Baker, A. D., eds.), Academic Press, New York, Vol. II, p. 2 (1978)Google Scholar
  5. 5.
    Photoemission in Solids I, General Principles (Cardona, M., Ley, L., eds.), Topics in Applied Physics, Vol. 26, Springer Verlag, Berlin 1978Google Scholar
  6. 6.
    Photoemission in Solids II, Case studies (Ley, L., Cardona, M., eds.), Topics in Applied Physics, Vol. 27, Springer Verlag, Berlin 1979Google Scholar
  7. 7.
    Handbook of X-Ray and Ultraviolet Photoelectron Spectroscopy (Briggs, D., ed.), Hayden and Sons Ltd., London 1977Google Scholar
  8. 8.
    Photoemission and the Electronic Properties of Surfaces (Feuerbacher, B., Fitton, B., Willis, R. F., eds.), John Wiley and Sons, Chichester 1978Google Scholar
  9. 9.
    Jørgensen, C. K., Berthou, H.: Mat. Fys. Medd. Dansk. Viddensk. Selskab. 38, 15 (1972)Google Scholar
  10. 10.
    Lang, J. K., Baer, Y.: Solid State Commun. 31, 945 (1979)Google Scholar
  11. 11.
    Cox, P. A.: Structure and Bonding 24, 59 (1975)Google Scholar
  12. 12.
    Cox, P. A., Lang, J. K., Baer, Y.: J. Phys. F11, 113 (1981)Google Scholar
  13. 13.
    Gerken, F.: J. Phys. F13, 703 (1983)Google Scholar
  14. 14.
    Jørgensen, C. K.: Structure and Bonding 22, 49 (1975).CrossRefGoogle Scholar
  15. 15.
    Veal, B. W. et al.: Phys. Rev. B15, 2929 (1977)Google Scholar
  16. 16.
    Gerken, F., Schmidt-May, J.: J. Phys. F13, 1571 (1983)Google Scholar
  17. 17.
    Lang, J. K., Baer, Y., Cox, P. A.: Phys. Rev. Letters 42, 74 (1979)Google Scholar
  18. 18.
    Baer, Y., Schoenes, J.: Solid State Commun. 33, 885 (1980)Google Scholar
  19. 19.
    Gadzuk, J. W.: Chapter V of Ref. 8Google Scholar
  20. 20.
    Kotani, A., Toyozawa, Y.: Japn. J. Phys. 37, 912 (1974)Google Scholar
  21. 21.
    Cohen-Tannoudji, C., Diu, B., Laloë, F.: Mécanique Quantique, Vol. 2, Hermann, Paris 1977Google Scholar
  22. 22.
    Scofield, J. H.: J. Electron Spectrosc. 8, 129 (1976)Google Scholar
  23. 23.
    Eastman, D. E., Kuznietz, M.: Phys. Rev. Letters 26, 846 (1971)Google Scholar
  24. 24.
    Baptist, R. et al.: Physica 102 B, 63 (1980)Google Scholar
  25. 25.
    Baer, Y.: in Actinides in Perspective (Edelstein, N. M., ed.), Pergamon Press, Oxford, p. 81 (1982)Google Scholar
  26. 26.
    Treglia, G., Ducastelle, F., Spanjaard, D.: J. Phys. (Paris) 41, 281 (1980)Google Scholar
  27. 27.
    Herbst, J. F., Watson, R. E., Lindgren, I.: Phys. Rev. B14, 3265 (1976)Google Scholar
  28. 28.
    Johansson, B., Skriver, H. L.: J. Magn. Magn. Mat. 29, 217 (1982)Google Scholar
  29. 29.
    Johansson, B.: to appear in Phys. Rev. BGoogle Scholar
  30. 30.
    Johansson, B. et al.: Physica 102 B, 12 (1980)Google Scholar
  31. 31.
    Mårtensson, N., Johansson, B.: Phys. Rev. Letters 45, 482 (1980)Google Scholar
  32. 32.
    Guillot, G., et al.: ibid. 39, 1632 (1977)Google Scholar
  33. 33.
    Hillebrecht, F. U. et al.: Phys. Rev. B 27, 2179 (1983)Google Scholar
  34. 34.
    Fuggle, J. C. et al.: Phys. Rev. Letters 45, 1597 (1980)Google Scholar
  35. 35.
    Nagakura, J., Ishii, T., Sagawa, T.: J. Phys. Soc. Jpn. 33, 754 (1972)Google Scholar
  36. 36.
    Fuggle, J. C. et al.: Phys. Rev. B 27, 7330 (1983)Google Scholar
  37. 37.
    Crecelius, G., Wertheim, G. K., Buchanan, D. N. E.: ibid. B 18, 6519 (1978)Google Scholar
  38. 38.
    Hillebrecht, F. U., Fuggle, J. C.: ibid. B 25, 3550 (1982)Google Scholar
  39. 39.
    Kotani, A., Toyozawa, Y.: J. Phys. Soc. Jpn. 35, 1073 (1973)Google Scholar
  40. 40.
    Johansson, B.: Phys. Rev. B11, 2740 (1975)Google Scholar
  41. 41.
    Fuggle, J. C. et al.: ibid. B 27, 2145 (1983)Google Scholar
  42. 42.
    Lundqvist, B. I.: Phys. Stat. Solidi 32, 273 (1969)Google Scholar
  43. 43.
    Seah, M. P., Dench, W. A.: Surf. Interf. Anal. 1, 2 (1980)Google Scholar
  44. 44.
    Steiner, P., Höchst, H., Hüfner, S.: Z. Phys. B30, 129 (1978)Google Scholar
  45. 45.
    Citrin, P. H., Wertheim, G. K., Baer, Y.: Phys. Rev. Letters 41, 1425 (1978)Google Scholar
  46. 46.
    Duc, T. M. et al.: ibid. 43, 789 (1979)Google Scholar
  47. 47.
    van der Veen, J. F. et al.: Solid State Commun. 37, 555 (1981)Google Scholar
  48. 48.
    Wertheim, G. K., and Campagna, M.: Chem. Phys. Letters 47, 182 (1977)Google Scholar
  49. 49.
    Allen, J. W. et al.: Phys. Rev. B21, 1335 (1980)Google Scholar
  50. 50.
    Tegart, W. J. McG.: The Electrolytic and Chemical Polishing of Metals in Research and Industry, Pergamon Press, London 1956Google Scholar
  51. 51.
    Musket, R. G. et al.: Appl. Surf. Sci. 10, 143 (1982)Google Scholar
  52. 52.
    Naegele, J. R. et al.: ibid. 4, 510 (1980)Google Scholar
  53. 53.
    Thiry, P. A. et al.: Phys. Rev. B29, 4824 (1984)Google Scholar
  54. 54.
    Urch, D. S., Weber, M.: J. Electron Spectrosc. 5, 791 (1974)Google Scholar
  55. 55.
    Naegele, J. R.: J. Phys. (Paris) 45, C2-841 (1984)Google Scholar
  56. 56.
    Baer, Y., Lang, J. K.: Phys. Rev. B21, 2060 (1980)Google Scholar
  57. 57.
    Skriver, H. L., Jan, J. P.: ibid. B21, 1489 (1980)Google Scholar
  58. 58.
    Schneider, W. D., Laubschat, C.: ibid. B23, 997 (1981)Google Scholar
  59. 59.
    Norton, P. R. et al.: ibid. B21, 2572 (1980)Google Scholar
  60. 60.
    Fuggle, J. C. et al.: J. Phys. F4, 335 (1974)Google Scholar
  61. 61.
    Veal, B. W., Lam, D. J.: Phys. Rev. B 10, 4902 (1974)Google Scholar
  62. 62.
    Verbist, J. et al.: J. Electron Spectrosc. 5, 193 (1974)Google Scholar
  63. 63.
    Nornes, S. B., Meisenheimer, R. G.: Surf. Sci. 88, 191 (1979)Google Scholar
  64. 64.
    Grohs, H. et al.: Solid State Commun. 33, 573 (1980)Google Scholar
  65. 65.
    Allen, G. C., Trickle, J. R., Tucker, P. M.: Phil. Mag. B 43, 689 (1981)Google Scholar
  66. 66.
    Greuter, F. et al.: Physica 102 B, 117 (1980)Google Scholar
  67. 67.
    Iwan, M., Koch, E. E., Himpsel, F. J.: Phys. Rev. B 24, 613 (1981)Google Scholar
  68. 68.
    Freeman, A. J., Koelling, D. D., Watson Yang, T. J.: J. Phys. (Paris) 40, C4-134 (1979)CrossRefGoogle Scholar
  69. 69.
    Skriver, H. L.: quoted in Ref. 56Google Scholar
  70. 70.
    The Actinides: Electronic Structure and Related Properties (Freeman, A. J., Darby Jr., I. B., eds.), Academic Press, New York 1974Google Scholar
  71. 71.
    Brodsky, M. B. et al.: in Ref. 70, vol. 2, p. 185Google Scholar
  72. 72.
    Dallacasa, V. J.: J. Phys. F11, 177 (1981)Google Scholar
  73. 73.
    Larson, D. T.: J. Vac., Sci. Technol. 17, 55 (1980)Google Scholar
  74. 74.
    Cox, L. E., Ward, J. W.: Inorg. Nucl. Chem. Letters 17, 265 (1981)Google Scholar
  75. 75.
    Baptist, R. et al.: J. Phys. F12, 2103 (1982)Google Scholar
  76. 76.
    Naegele, J. R. et al.: in Proceedings of the 12ème Journées des Actinides, Orsay (France) 1982Google Scholar
  77. 77.
    Skriver, H. L., Andersen, O. K., Johansson, B.: Phys. Rev. Letters 41, 42 (1978)Google Scholar
  78. 78.
    Skriver, H. L., Andersen, O. K., Johansson, B.: ibid. 44, 1230 (1980)Google Scholar
  79. 79.
    Beatham, N. et al.: Chem. Phys. Letters 63, 69 (1979)Google Scholar
  80. 80.
    Lawrence, J. M. et al.: Phys. Rev. B26, 2362 (1982)Google Scholar
  81. 81.
    Reihl, B. et al.: ibid. B26, 1842 (1982)Google Scholar
  82. 82.
    Allen, J. W. et al.: Phys. Rev. Letters 46, 1100 (1981)Google Scholar
  83. 83.
    Peterman, D. J. et al.: Phys. Rev. B27, 808 (1983)Google Scholar
  84. 84.
    Zangwill, A., Soven, P.: Phys. Rev. Letters 45, 204 (1980)Google Scholar
  85. 85.
    Freeman, A. J., Koelling, D. D.: in Ref. 70, Vol. I, p. 51Google Scholar
  86. 86.
    Naegele, J. R. et al.: Phys. Rev. Letters 52, 1834 (1984)Google Scholar
  87. 87.
    Herbst, J. F.: Physica Scripta 21, 553 (1980)Google Scholar
  88. 88.
    Wertheim, G. K., Crecelius, G.: Phys. Rev. Letters 40, 813 (1978)Google Scholar
  89. 89.
    89. Brooks, M. S. S.: private communicationGoogle Scholar
  90. 90.
    Brodsky, M. B.: Rep. Progr. Phys. 41, 1547 (1978)Google Scholar
  91. 91.
    Gordon, J. E. et al.: Proc. R. Soc., London A 351, 179 (1976)Google Scholar
  92. 92.
    Stewart, G. R., Eliott, R. O.: Actinides 81, LBL report 12441, 206 (1981)Google Scholar
  93. 93.
    McLean, W. et al.: Phys. Rev. B 25, 8 (1982)Google Scholar
  94. 94.
    Doniach, S., Šunjić, M.: J. Phys. C3, 284 (1970)Google Scholar
  95. 95.
    Schonhammer, K., Gunnarsson, O.: Z. Phys. B30, 297 (1978)Google Scholar
  96. 96.
    Larson, D. T., Haschke, J. M.: Inorg. Chem. 20, 1945 (1981)Google Scholar
  97. 97.
    Wertheim, G. K., Campagna, M.: Solid State Commun. 26, 553 (1978)Google Scholar
  98. 98.
    Johansson, B., Mårtensson, N.: Phys. Rev. B24, 4484 (1981)Google Scholar
  99. 99.
    Brooks, M. S. S., Kelly, P. J.: Solid State Comm. 45, 689 (1983)Google Scholar
  100. 100.
    Kelly, P. J.: PhD-Thesis, Portsmouth Polytechnic 1980Google Scholar
  101. 101.
    Kelly, P. J., Brooks, M. S. S.: Physica 102 B, 81 (1980)Google Scholar
  102. 102.
    Gubanov, V. A., Rosen, A., Ellis, D. E.: Solid State Commun. 22, 219 (1977)Google Scholar
  103. 103.
    Weber, J., Gubanov, V. A.: J. Inorg. Nucl. Chem. 41, 693 (1979)Google Scholar
  104. 104.
    Gubanov, V. A., Rosen, A., Ellis, D. E.: ibid. 41, 975 (1979)Google Scholar
  105. 105.
    Ellis, D. E., Gubanov, V. A., Rosen, D. E.: J. Phys. (Paris) 40, C4-187 (1979)Google Scholar
  106. 106.
    Blank, H.: in: Thermodynamics of Nuclear Materials, 1974, Vol. II, IAEA-Vienna, 45 (1975)Google Scholar
  107. 107.
    Manes, L.: A new method of statistical thermodynamics and its application to oxides of the lanthanide and actinide series, in “Nonstoichiometric oxides” (Sorensen, O. T. ed.), Academic Press, New York, Chapt. 3, 99 (1981)Google Scholar
  108. 108.
    Veal, B. W., Lam, D. J.: in Gmelin Handbook of Inorganic Chemistry, System Nr. 55, Uranium, Suppl., Vol. A 5, Springer Verlag, Berlin, p. 176 (1982)Google Scholar
  109. 109.
    Manes, L., Naegele, J. R.: in: Plutonium 1975 and Other Actinides (Blank, H., Lindner, R., eds.), North-Holland, Amsterdam, p. 361 (1976)Google Scholar
  110. 110.
    Schoenes, J.: Phys. Rep. 63, 301 (1980)Google Scholar
  111. 111.
    Teterin, Yu. A. et al.: Phys. Chem. Minerals 7, 151 (1981)Google Scholar
  112. 112.
    Naegele, J. R., Manes, L.: private communicationGoogle Scholar
  113. 113.
    Veal, B. W., Arko, A. J., Weber, L. W.: Actinides 1981, LBL-report 12441, p. 66 (1981)Google Scholar
  114. 114.
    Chauvet, G., Baptist, R.: Solid State Commun. 43, 793 (1982)Google Scholar
  115. 115.
    Davis, L. C., Feldkamp, L. A.: Phys. Rev. B23, 6239 (1981)Google Scholar
  116. 116.
    Naegele, J. R., Manes, L.: Actinides 1981, LBL-report 12441, p. 69 (1981)Google Scholar
  117. 117.
    Courteix, D. et al.: Solid State Commun. 39, 209 (1981)Google Scholar
  118. 118.
    Lohr, L. L., Hotokka, M., Pyykkö, P.: Quantum Chemistry Program Exchange, QCPE, 12, 387 (1980)Google Scholar
  119. 119.
    Manes, L., Buijs, K., Schippa, B.: in: Transplutonium 1975, North-Holland, Amsterdam, 257 (1976)Google Scholar
  120. 120.
    Veal, B. W. et al.: Proc. 2nd Int. Conf. Electr. Struct. Actinides, Wroclaw 1977Google Scholar
  121. 121.
    Veal, B. W. et al.: in: Plutonium 1975 and Other Actinides (Blank, H., Lindner, R. eds.), North-Holland, Amsterdam, 383 (1976)Google Scholar
  122. 122.
    Schneider, W. D., Laubschat, C.: Phys. Rev. Letters 46, 1023 (1981)Google Scholar
  123. 123.
    Cox, L. E.: J. Electron Spectrosc. 26, 167 (1982)Google Scholar
  124. 124.
    Gubanov, V. A., Rosén, A., Ellis, D. E.: J. Phys. Chem. Solids 40, 17 (1979)Google Scholar
  125. 125.
    Pireaux, J. J. et al.: Chem. Phys. 22, 113 (1977)Google Scholar
  126. 126.
    Larsson, S.: Physica Scripta 16, 378 (1977)Google Scholar
  127. 127.
    Bancroft, G. M. et al.: Phys. Chem. Letters 51, 105 (1977)Google Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 1985

Authors and Affiliations

  • J. R. Naegele
    • 1
  • J. Ghijsen
    • 1
  • L. Manes
    • 1
  1. 1.Commission of the European Communities, Joint Research Centre, Karlsruhe EstablishmentEuropean Institute for Transuranium ElementsKarlsruheGermany

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