Skutterudite vs. ReO₃ structures for MX₃ solids: electronic requirements ‡

Abstract

Electronic band-structure calculations on ReO₃ and CoP₃ have been performed to analyse the different structural preferences found for these two compounds. The electronic origin of these differences is associated with the formation of the characteristic non-metal four-membered rings of the skutterudite structure, which is energetically unfavorable for compounds with small, strongly electronegative anions. The combination of two factors has been identified to be responsible for the structural differences between these compounds. The first is the electronegativity difference between the two types of atoms that form the solid: for strongly electronegative non-metal atoms like O or F the ReO₃-type structure is expected to be the most stable, while for the combination of less electronegative atoms like the pnictides with late transition metals the skutterudite structure is preferred. The second factor is the relative size of the constituting atoms: small atoms like F and O favor the ReO₃ structure, while larger atoms like P and As stabilize the skutterudite one.

References

1. P. Villars and L. D. Calvert, Pearson's Handbook of Crystallographic Data for Intermetallic Phases, American Society for Metals, Metals Park, Ohio, 1986.
2. D. Jung, M.-H. Whangbo and S. Alvarez, Inorg. Chem., 1990, 29, 2252.
3. D. J. Singh and W. E. Pickett, Phys. Rev. B, 1994, 50, 11 235.
4. M. Llunell, P. Alemany, S. Alvarez, V. P. Zhukov and A. Vernes, Phys. Rev. B, 1996, 53, 10 605.
5. K. Meisel, Z. Anorg. Allg. Chem., 1932, 207, 121.
6. T.-S. Chang and P. Trucano, J. Appl. Crystallogr., 1978, 11, 286.
7. I. Oftedal, Z. Kristallogr., 1928, A66, 517.
8. S. Rundqvist and N.-O. Ersson, Ark. Kemi, 1968, 30, 103.
9. A. Kjekshus and T. Rakke, Acta Chem. Scand., Ser. A, 1974, 28, 99.
10. N. Mandel and J. Donohue, Acta Crystallogr., Sect. B, 1971, 27, 2288.
11. R. T. M. Dobbe, W. J. Lustenhouwer, M. A. Zakrzewski, K. Goubitz, J. Fraanje and H. Schenk, Can. Mineral., 1994, 32, 179.
12. W. Jeitschko and D. J. Braun, Acta Crystallogr., Sect. B, 1977, 33, 3401.
13. D. J. Braun and W. Jeitschko, J. Solid State Chem., 1980, 32, 357.
14. D. J. Braun and W. Jeitschko, J. Less-Common Met., 1980, 72, 147.
15. D. J. Braun and W. Jeitschko, J. Less-Common Met., 1980, 76, 33.
16. N. T. Stetson, S. M. Kauzlarich and H. Hope, J. Solid State Chem., 1991, 91, 140.
17. C. B. H. Evers, L. Boonk and W. Jeitschko, Z. Anorg. Allg. Chem., 1994, 620, 1028.
18. R. Korenstein, S. Soled, A. Wold and G. Collin, Inorg. Chem., 1977, 16, 2344.
19. V. Gutmann and K. H. Jack, Acta Crystallogr., 1951, 4, 244.
20. P. Ehrlich, F. Ploeger and G. Pietzka, Z. Anorg. Allg. Chem., 1955, 282, 19.
21. M. Pouchard, M. R. Torki, G. Demazeau and P. Hagenmuller, C.R. Acad. Sci., Ser. C, 1971, 273, 1093.
22. J. E. Schirber, B. Morosin, R. W. Alkire, A. C. Larson and P. J. Vergamini, Phys. Rev. B, 1984, 29, 4150.
23. M. T. Weller and P. G. Dickens, J. Solid State Chem., 1985, 58, 164.
24. J. B. Parise, E. M. I. McCarron and A. W. Sleight, Mater. Res. Bull., 1987, 22, 803.
25. P. G. Dickens and M. T. Weller, J. Solid State Chem., 1983, 48, 407.
26. J.-L. Fourquet, M.-F. Renou, R. DePape, H. Theveneau, P. P. Man, O. Lucas and J. Pannetier, Solid State Ionics, 1983, 9, 1011.
27. J.-L. Fourquet, M.-F. Renou and R. DePape, Rev. Chim. Miner., 1984, 21, 383.
28. P. J. Wiseman and P. G. Dickens, J. Solid State Chem., 1973, 6, 374.
29. P. J. Wiseman and P. G. Dickens, J. Solid State Chem., 1976, 17, 91.
30. R. J. Cava, A. Santoro, D. W. Murphy, S. M. Zahurak and R. S. Roth, J. Solid State Chem., 1983, 50, 121.
31. Inorganic Crystal Structure Database, Release 96/1, FIZ Karlsruhe and Gmelin-Institut, 1996.
32. N. N. Zhuravlev, G. S. Zhdanov and R. N. Kuz'min, Kristallografiya, 1960, 5, 553.
33. R. N. Kuz'min and G. S. Zhdanov, Kristallografiya, 1960, 5, 869.
34. A. Lyons, R. P. Gruska, C. Case, S. N. Subbarao and A. Wold, Mater. Res. Bull., 1978, 13, 125.
35. G. A. Slack and V. G. Tsoukala, J. Appl. Phys., 1994, 76, 1165.
36. C. M. Pleass and R. D. Heyding, Can. J. Chem., 1962, 40, 590.
37. L. D. Dudkin and N. K. Abrikosov, Zh. Neorg. Khim., 1957, 2, 212.
38. V. I. Zobnina and L. D. Dudkin, Fiz. Tverd. Tela, 1959, 1, 1821.
39. F. Corà, M. G. Stachiotti, C. R. A. Catlow and C. O. Rodriguez, J. Phys. Chem. B, 1997, 101, 3945.
40. J. L. Feldman and D. J. Singh, Phys. Rev. B, 1996, 53, 6273.
41. D. J. Singh and I. I. Mazin, Phys. Rev. B, 1997, 56, R1650.
42. R. Hoffmann, J. Chem. Phys., 1963, 39, 1397.
43. M.-H. Whangbo and R. Hoffmann, J. Am. Chem. Soc., 1978, 100, 6093.
44. M.-H. Whangbo, R. Hoffmann and R. B. Woodward, Proc. R. Soc. London, Ser. A, 1979, 366, 23.
45. R. Hoffmann, Solids and Surfaces: A Chemist's View of Bonding in Extended Structures, VCH, Weinheim, 1988.
46. T. A. Albright, J. K. Burdett and M. H. Whangbo, Orbital Interactions in Chemistry, Wiley, New York, 1985.
47. M. Llunell, S. Alvarez, P. Alemany and R. Hoffmann, Inorg. Chem., 1996, 35, 4683.
48. J. H. Ammeter, H. B. Bürgi, J. C. Thibeault and R. Hoffmann, J. Am. Chem. Soc., 1978, 100, 3686.
49. A. Dedieu, T. A. Albright and R. Hoffmann, J. Am. Chem. Soc., 1979, 101, 3141.
50. S. Alvarez, Table of Parameters for Extended Hückel Calculations, Universitat de Barcelona, 1993.
51. R. Ramírez and M. C. Böhm, Int. J. Quantum Chem., 1986, 30, 391; 1988, 34, 571.