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Structural and thermodynamic properties of actinide solids and their relation to bonding

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Actinides — Chemistry and Physical Properties

Part of the book series: Structure and Bonding ((STRUCTURE,volume 59/60))

Abstract

The problem of bonding in actinide solids has been approached through the establishment of semi-theoretical correlations between thermodynamic and structural properties and the degree of participation to the bond of the different electronic orbitals of the actinide atom.

The first part of the chapter is devoted to an analysis of these correlations, as well as to the presentation of the most important experimental results. In a second part the following stage of development is reviewed, i.e. the introduction of more quantitative theories mostly based on bond structure calculations. These theories are given a thermodynamic form (equation of states at zero temperature), and explain the typical behaviour of such ground state properties as cohesive energies, atomic volumes, and bulk moduli across the series. They employ in their simplest form the Friedel model extended from the d- to the 5 f-itinerant state. The Mott transition (between plutonium and americium metals) finds a good justification within this frame.

In actinide binary compounds an equation of state can also be developed on the same lines. The difference in electronegativity of the actinide and the non-actinide element plays an important role, determining the degree of mixing between the actinide orbitals (5 f and 6 d) and the orbitals of the ligand. A mixture of metallic, ionic and covalent bond is then encountered. In the chapter, two classes of actinide compounds are reviewed: NaCl-structure pnictides or chalcogenides, and oxides.

In oxides a large departure from the stoichiometric composition is usually met. The importance of this phenomenon, also for the understanding of the oxide bond, is highlighted at the end of the chapter.

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References

  1. Pearson, W. B.: The Crystal Chemistry and Physics of Metals and Alloys, Wiley 1972

    Google Scholar 

  2. Brewer, L.: Science 161, 115–122 (1968)

    Article  CAS  Google Scholar 

  3. Fournier, J. M.: J. Phys. Chem. Solids 37, 235–244 (1976)

    Article  CAS  Google Scholar 

  4. Johansson, B., Rosengren, A.: Phys. Rev. B11, 1367 (1975)

    Google Scholar 

  5. Johansson, B.: ibid. B11, 2740 (1975)

    Google Scholar 

  6. Hume-Rothery, W.: The Engel-Brewer Theories of Metals and Alloys, Progress in Materials Science, Vol. 13 (eds. Chalmers, B., Hume-Rothery, W.), Pergamon Press, Oxford, 231–264 (1968)

    Google Scholar 

  7. Brooks, M. S. S., Johansson, B.: J. Phys. F: Met. Phys. 13, L197 (1983)

    Article  CAS  Google Scholar 

  8. Wyckoff, R. W. G.: Crystal Structures, 2nd edition, Interscience Publishers 1965

    Google Scholar 

  9. Gschneidner, K. A., jr.: p. 275–430 of: Solid State Physics, Vol. 16 (eds. Seitz, F., Turnbull, D.), Academic Press, New York 1964

    Google Scholar 

  10. Johansson, B., Skriver, H. L., Anderson, O. K.: p. 245–262 of: Physics of Solids under High Pressure (eds. Schilling, J. S., Shelton, R. N.) North-Holland Publ. Co. 1981

    Google Scholar 

  11. Fournier, J. M.: These Dr.-ès-Sc., Grenoble 1975

    Google Scholar 

  12. Donohue, J.: The Structures of the Elements, reprint edition 1982, Robert E. Krieger Publ. Co. Malabar, Florida

    Google Scholar 

  13. Bellussi, G., Benedict, U., Holzapfel, W. B.: J. Less-Common Metals 78, 147 (1981)

    Article  CAS  Google Scholar 

  14. Benjamin, T. M. et al.: Carnegie Institution of Washington Year Book 80, 280 (1981)

    Google Scholar 

  15. Benedict, U. et al.: J. Magn. and Magn. Mat. 29, 287 (1982)

    Article  CAS  Google Scholar 

  16. Akella, J., G. S. Smith, H. Weed: J. Phys. Chem. Solids, submitted

    Google Scholar 

  17. Stephens, D. R.: J. Phys. Chem. Solids 27, 1201 (1966)

    Article  CAS  Google Scholar 

  18. Roof, R. B.: p. 221–230 of: Advances in X-ray Analysis 24, Plenum Press 1981

    CAS  Google Scholar 

  19. Akella, J. et al.: J. Geophys. Research 85, 7056 (1980)

    CAS  Google Scholar 

  20. Smith, G. S. et al.: paper presented at Actinides 1981, Asilomar, CA, Sept. 1981

    Google Scholar 

  21. Roof, R. B. et al.: Science 27, 1353 (1980)

    Google Scholar 

  22. Roof, R. B.: J. Appl. Cryst. 14, 447 (1981)

    Article  CAS  Google Scholar 

  23. Akella, J.: Report on the Workshop “Actinides under Pressure”, April 21–22, 1983, Commission of the European Communities, Joint Research Centre, Karlsruhe, 1983, p. 5

    Google Scholar 

  24. Benedict, U. et al.: J. Phys. F: Metal Phys. 14, L43 (1984)

    Article  CAS  Google Scholar 

  25. Smith, G. S., Akella, J.: J. Appl. Phys. 53, 9212 (1982)

    Article  CAS  Google Scholar 

  26. Grosshans, W. A., Vohra, Y. K., Holzapfel, W. B.: J. Phys. F: Metal Phys. 13, L147 (1983)

    Article  CAS  Google Scholar 

  27. Roof, R. B.: Z. Krist. 158, 307 (1982)

    CAS  Google Scholar 

  28. Benedict, U. et al., in: Americium and Curium Chemistry, N. Edelstein, J. D. Navratil, W. W. Schulz, eds., Reidel Publ. Co., Dordrecht, in press.

    Google Scholar 

  29. Brooks, M. S. S.: J. Phys. F: Metal Phys. 13, 103 (1983)

    Article  CAS  Google Scholar 

  30. Smith, J. L., Kmetko, E. A.: J. Less-Common Metals 90, 83 (1983)

    Article  CAS  Google Scholar 

  31. Zachariasen, W. H.: in: The Metal Plutonium (ed. Coffinberry, A. S., Miner, W. N.), Univ. of Chicago Press, p. 99, Chicago 1961

    Google Scholar 

  32. Nugent, L. J., Burnett, J. L., Morss, L. R.: J. Chem. Thermodyn. 5, 665 (1973)

    Article  CAS  Google Scholar 

  33. Carlsson, T. A. et al.: Atomic Data 2, 63 (1970)

    Article  Google Scholar 

  34. Bonnelle, C., Lachere, G.: J. de Physique 35, 295 (1974)

    Article  CAS  Google Scholar 

  35. Skriver, H. L., Andersen, O. K., Johansson, B.: Phys. Rev. Letters 44, 1230 (1980)

    Article  CAS  Google Scholar 

  36. Jullien, R., Galleani d'Agliano, E., Coqblin, B.: Phys. Rev. B6, 2139 (1972)

    Google Scholar 

  37. Johansson, B., Skriver, H. L.: J. of Magn. and Magn. Mat. 29, 217 (1982)

    Article  CAS  Google Scholar 

  38. Skriver, H. L., Andersen, E. K., Johansson, B.: Phys. Rev. Lett. 41, 42 (1978)

    Article  CAS  Google Scholar 

  39. Brooks, M. S. S.: J. Phys. F13, 103 (1982)

    Google Scholar 

  40. Brooks, M. S. S.: J. Phys. F: Metl. Phys. 14, 1157 (1984)

    Article  CAS  Google Scholar 

  41. Friedel, J.: in: The Physics of Metals (ed. Ziman, J.), Cambridge University Press, London, Ch. 8 (1969)

    Google Scholar 

  42. Murnaghan, F. D.: American J. of Math. LIX, 235 (1937)

    Article  Google Scholar 

  43. Harrison, W. A.: in: Electronic Structure and the Properties of Solids. The physics of the chemical bond (eds. Freeman, W. H., Co.), San Francisco 1980

    Google Scholar 

  44. Jorgensen, Ch. K.: in: Orbitals in Atoms and Molecules, Academic Press, London and New York 1962

    Google Scholar 

  45. Nugent, J. L.: J. Inorg. Nucl. Chem. 32, 3485 (1970)

    Article  CAS  Google Scholar 

  46. Nugent, J. L. et al.: ibid. 33, 2503 (1971)

    Article  CAS  Google Scholar 

  47. Bradbury, M. J.: J. Less-Common Met. 78, 207 (1981)

    Article  CAS  Google Scholar 

  48. Belle, J.: J. Nucl. Mats. 30, 3 (1969)

    Article  CAS  Google Scholar 

  49. Willis, B. T. M.: Proc. Roy. Soc. (London) A274, 133 (1963)

    Google Scholar 

  50. Markin, T. L., Wheeler, V. J., Brones, R. J.: J. Inorg. Nucl. Chem. 30, 807 (1968)

    Article  CAS  Google Scholar 

  51. Matzke, Hj., Davies, J. A., Johansson, G. E.: Can. J. Phys. 49, 2215 (1971)

    CAS  Google Scholar 

  52. Matzke, Hj.: Diffusion in non-stoichiometric oxides, Chapt. 4 of Non-stoichiometric Oxides (ed. Sorensen, O. J.), Academic Press, New York 1981

    Google Scholar 

  53. Faber, J. Jr., Seitz, M. A., Mueller, M. H.: J. Phys. Chem. Solids 37, 903 (1976) ibid. 909 (1976)

    Article  CAS  Google Scholar 

  54. Blank, H.: in: Thermodynamics of Nuclear Materials, 1974, Vol. II IAEA-Vienna, 45 (1975)

    Google Scholar 

  55. Turcotte, R. P., Chikalla, T. D.: J. Inorg. Nucl. Chem. 35, 3739 (1971)

    Google Scholar 

  56. Turcotte, R. P., Chikalla, T. D., Eyring,L.: ibid. 35, 809 (1973)

    Article  CAS  Google Scholar 

  57. Andersen, O. K., Klose, W., Nohl, H.: Phys. Rev. B17, 1209 (1978)

    Google Scholar 

  58. Andersen, O. K. et al.: Pure and Appl. Chem. 52, 93 (1979)

    Google Scholar 

  59. Brooks, M. S. S., Glötzel, D.: Physica 102 B, 51 (1980)

    Google Scholar 

  60. Brooks, M. S. S.: J. Phys. F: Metal Phys. 14, 653 (1984)

    Article  CAS  Google Scholar 

  61. Brooks, M. S. S. et al.: Physica 102 B, 84 (1980)

    Google Scholar 

  62. Kelly, P. J., Brooks, M. S. S., Allen, R.: J. de Phys. C4, C4-184 (1979)

    Google Scholar 

  63. Kelly, P. J., Brooks, M. S. S.: Physica 102 B, 81 (1980)

    Google Scholar 

  64. Brooks, M. S. S., Kelly, P. J.: Solid State Comm. 45, 689 (1983)

    Article  CAS  Google Scholar 

  65. Gubanov, V. A., Ellis, D. E., Freeman, A. J.: Fiz. Tverd. Tela 19, 409 (1977)

    CAS  Google Scholar 

  66. Gubanov, V. A., Rosén, A., Ellis, D. E.: Solid State Comm. 22, 219 (1977)

    Article  CAS  Google Scholar 

  67. Ellis, D. E., Gubanov, V. A., Rosén, A.: J. de Phys. C4, Ca-187 (1979)

    Google Scholar 

  68. Gubanov, V. A., Rosén, A., Ellis, D. E.: J. Phys. Chem. Solids 40, 17 (1979)

    Article  CAS  Google Scholar 

  69. Gubanov, V. A., Rosén, A., Ellis, D. E.: J. Inorg. Nucl. Chem. 41, 975 (1979)

    Article  CAS  Google Scholar 

  70. Programme Progress Report “Plutonium Fuels and Actinide Research”, TUSR 27, Joint Research Center of the European Community, p. 102 (1979)

    Google Scholar 

  71. Manes, L., Barisich, A.: Phys. Stat. Sol. (a) 3, 971 (1970)

    Article  CAS  Google Scholar 

  72. Manes, L., Naegele, J.: in: Plutonium 1975 and Other Actinides (eds. Blank, H., Lindner, R.), North-Holland, Amsterdam, 361 (1976)

    Google Scholar 

  73. Manes, L.: A new method of statistical thermodynamics and its application to oxides of the lanthanide and actinide series, in “Non-stoichiometric Oxides” (ed. Sørensen, O. T.), Academic Press, New York, Chapt. 3, p. 99 (1981)

    Google Scholar 

  74. Stoneham, A. M.: Theory of Defects in Solids, Clarendon Press, Oxford 1975

    Google Scholar 

  75. Willis, B. T. M.: Proc. Br. Ceram. Soc. (London) 1, 9 (1964)

    Google Scholar 

  76. Willis, B. T. M.: J. de Phys. 25, 431 (1964)

    CAS  Google Scholar 

  77. Willis, B. T. M.: Acta Crystallogr. 18, 75 (1965)

    Article  CAS  Google Scholar 

  78. Cheetham, A. K. et al.: Solid State Commun. 8, 171 (1970)

    Article  CAS  Google Scholar 

  79. Cheetham, A. K.: in: Chemical applications of thermal neutron scattering (ed. Willis, B. T. M.), Oxford University Press, London and New York 1973

    Google Scholar 

  80. Sørensen, O. T.: Thermodynamics and defect structure of non-stoichiometric oxides, in “Nonstoichiometric oxides” (ed. Sørensen, O. T.), Academic Press, New York, Chapt. 1, p. 1 (1981)

    Google Scholar 

  81. Catlow, C. R. A.: J. de Phys. C6, L64 (1973)

    Article  Google Scholar 

  82. Catlow, C. R. A.: Defect clustering in non-stoichiometric oxides, in “Non-stoichiometric oxides” (ed. Sørensen, O. T.), Academic Press, New York, Chapt. 2, p. 60 (1981)

    Google Scholar 

  83. Hyde, B. G., Eyring, L.: Proc. Conf. Rare Earth Res. 4th, 623 (1964)

    Google Scholar 

  84. Sawyer, J. O., Hyde, B. G., Eyring, L.: Bull. Soc. Chim. Fr. 1190 (1965)

    Google Scholar 

  85. Kunzmann, P., Eyring, L.: J. Solid State Chem. 14, 229 (1975)

    Article  CAS  Google Scholar 

  86. Summerville, E., Tuenge, R. T., Eyring, L.: ibid. 24, 21 (1978)

    Article  CAS  Google Scholar 

  87. Manes, L., Manes-Pozzi, B.: in: Plutonium 1975 and other actinides (eds. Blank, H., Linder, R.), North-Holland, Amsterdam, 145 (1976)

    Google Scholar 

  88. Schmitz, F.: J. Nucl. Mater. 58, 357 (1975)

    Article  CAS  Google Scholar 

  89. Catlow, C. R. A.: ibid. 67, 336 (1977)

    Article  Google Scholar 

  90. De Franco, A., Gatesoupe, J. P.: in: Plutonium 1975 and other actinides (eds. Blank, H., Lindner, R.), North-Holland, Amsterdam, 135 (1971)

    Google Scholar 

  91. Manes, L. et al.: in: Thermodynamics of Nuclear Materials, 1979, Vol. I, IAEA-Vienna, 405 (1980)

    Google Scholar 

  92. Blank, H.: EUR 3653 e, EURATOM, European Atomic Energy Community, Bruxelles 1965

    Google Scholar 

  93. Blank, H.: J. Nucl. Mater. 51, 269 (1974)

    Article  CAS  Google Scholar 

  94. Benedict, U. et al., J. Phys. F: Metal Phys. 15, 29 (1985)

    Article  Google Scholar 

  95. Haire, R. G. et al., J. Less Common Metals, submitted

    Google Scholar 

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  1. Commission of the European Communities, Joint Research Centre, Karlsruhe Establishment, European Institute for Transuranium Elements, Postfach 2266, 7500, Karlsruhe, F. R. G.

    L. Manes & U. Benedict

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  1. L. Manes
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  2. U. Benedict
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Manes, L., Benedict, U. (1985). Structural and thermodynamic properties of actinide solids and their relation to bonding. In: Manes, L. (eds) Actinides — Chemistry and Physical Properties. Structure and Bonding, vol 59/60. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3-540-13752-1_3

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  • DOI: https://doi.org/10.1007/3-540-13752-1_3

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