Abstract
Experiments on LaCoO3 demonstrate that crystal-field theory and band theory describe two thermodynamically different electronic phases. For an integral number of electrons per atom, the phase transition is first-order. The critical parameter is an overlap integral, which may be either a cation-cation or a cation-anion-cation overlap integral. Intra-atomic exchange and electron-phonon interactions contribute significantly to electron localization. The characteristic feature of collective electrons is a Fermi surface. Those physical properties that depend upon the existence of a Fermi surface vary discontinuously through a localized-electron ⇄ collective-electron transition; other physical properties, including electron mobility and paramagnetic susceptibility, apparently do not. It is argued that the spontaneous crystallographic distortions associated with semiconducting ⇄ metallic phase changes manifest the existence of narrow, cation-sublattice bands if the cations are removed from the centers of symmetry of their interstices, narrow crystalline bands otherwise; ferroelectric and antiferroelectric transitions manifest the existence of a narrow valence band; the formation of a homologous series of shear structures in nonstoichiometric compounds manifests narrow conduction bands. These distortions all result from the creation, or enhancement, of an energy discontinuity at the Fermi surface. By contrast, conventional Jahn-Teller distortions, magnetostriction due to spin-orbit coupling, and the ordering of small polarons manifest localized electrons and the applicability of crystal-field theory. It is also shown that the critical overlap integral (or bandwidth) for spontaneous band magnetism is only a little larger than that for a localized-electron ⇄ collective-electron transition. Preliminary data are compatible with two possibilities for bands that are more than half-filled: (1) saturation of orbitals ofα spin, which leads to localized electrons ofα spin and collective electrons ofβ spin; (2) spontaneous magnetization (ferromagnetism) of only the antibonding electrons, which may lead to reduced atomic moments. Spontaneous band antiferromagnetism may be stabilized in bands that are half-filled or slightly less. It is represented by a spin-density wave with wavelength adjusted to create an energy discontinuity at the Fermi surface. Spin-density waves are also possible among collectiveβ-spin electrons that are coupled to localizedα-spin electrons.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
Goodenough J. B.: J. Phys. Soc. Japan17 (1962), Suppl. B-I, 185.
Verwey E. J. W., Haayman P. W., Romeijn F. C.: J. Chem. Phys.15 (1947), 181.
Vallet P., Raccah P. M.: Compt. Rend. Acad. Sci. (Paris)258 (1964), 3679;
Carel C., Weigel D., Vallet P.: Compt. Rend. Acad. Sci. (Paris)260 (1965), 4325.
Goodenough J. B.: Bull. Soc. Chim. France4 (1965), 1200.
Goodenough J. B.: Description of Transition-Metal Compounds: Applications to Several Sulfides. Paper presented at Colloque International sur des Dérives Semi-métalliques, Université de Paris 1965.
Bertaut E. F.: Bull. Soc. Fr. Minéral. et Cryst.79 (1956), 276.
Goodenough J. B.: J. Appl. Phys.33 (1962), Suppl., 1197.
Adler D.: Ph. D. Thesis. Physics Department, Harvard University, Cambridge, Mass., 1964.
Pauling L.: The Nature of the Chemical Bond, 3rd ed. Cornell University Press, Ithaca (New York) 1960.
Andersson S., Magnéli A.: Naturwiss.43 (1956), 495; Acta chem. Scand.11 (1950), 164.
Gado P., Holmberg B., Magnéli A.: Acta chem. Scand.19 (1965), 2010.
Magnéli A.: Acta cryst.6 (1953), 495.
Sawyer J. O., Hyde B. G., Eyring L.: Bull. Soc. Chim. France4 (1965), 1190; Hyde B. G., Bevan D. J. M., Eyring L.: Phil. Trans. Roy. Soc. (London)A 259 (1966), 583.
Magnéli A.: Nature115 (1950), 356; Arkiv Kemi1 (1950), 513.
Overhauser A. W.: J. Phys. Chem. Solids3 (1957), 311.
Sato J., Toth R. S.: Phys. Rev.124 (1961), 1833;127 (1962), 469.
Kaplan T. A.: Phys. Rev.124 (1961), 329; J. Phys. Soc. Japan17 (1962), Suppl. B-I, 3.
Villain J.: J. Phys. Chem. Solids11 (1959), 303.
Yoshimori A.: J. Phys. Soc. Japan14 (1959), 807.
Fröhlich H., Sewell G. L.: Proc. Phys. Soc. (London)74 (1959), 643.
Holstein T.: Ann. of Phys.8 (1959), 325, 343.
Jonker G. H., van Houten S.: Halbleiterprobleme, Band VI (hrsg. von F. Sauter Friedr. Vieweg und Sohn, Braunschweig 1961, 118.
Jonker G. H.: J. Phys. Chem. Solids9 (1959), 165.
Shanks H. R., Sidles P. H., Danielson G. C.: Electrical Properties of the Tungsten Bronzes (Paper 22 in Nonstoichiometric Compounds, ed. by R. Ward; published as Advances in Chemistry Series 39). American Chemical Society, Washington D.C. 1963.
Ferretti A., Rogers D. B., Goodenough J. B.: J. Phys. Chem. Solids26 (1965), 2007.
Feinleib J., Scouler W. T., Ferretti A.: Bull. Am. Phys. Soc.11 (1966), 264.
Frederikse H. P. R., Thurber W. R., Hosler W. R.: Phys. Rev.134 (1964), A442.
Johnston W. D., Sestrich D.: J. Inorg. Nucl. Chem.20 (1961), 32;
Reuter B., Wollnik M.: Naturwiss.17 (1963), 589;
bKern S., Rogers D. B. (unpublished research).
Brixner L. M.: J. Inorg. Nucl. Chem.14 (1960), 225.
Goodenough J. B., Raccah P. M.: J. Appl. Phys.36 (1965), Suppl., 1031.
Raccah P. M. (personal communication).
Rogers D. B., Ferretti A., Arnott R. J., Goodenough J. B.: J. Appl. Phys.37 (1966), Suppl., 1431.
Goodenough J. B.: Magnetism and the Chemical Bond. Interscience Publishers, New York-London 1963.
Goodenough J. B.: Phys. Rev.100 (1955), 564.
Goodenough J. B.: J. Appl. Phys.37 (1966), Suppl., 1415.
Callaghan A., Moeller C. W., Ward R.: Inorg. Chem.5 (1966), 1572.
Longo J. M. (personal communication).
Goodenough J. B.: J. Phys. Chem. Solids6 (1958), 287.
Raccah P. M., Goodenough J. B.: Phys. Rev. (to be published).
Menyuk N., Dwight K., Raccah P. M.: J. Phys. Chem. Solids (to be published).
Landau L. D., Lifshitz E. M.: Statistical Physics. Pergamon Press, London 1958, 439.
MacChesney J. B., Sherwood R. C., Potter J. F.: J. Chem. Phys.43 (1965), 1907.
Foner S. (personal communication).
Longo J. M., Raccah P. M. (personal communícation).
Stoner E. C.: Proc. Roy. Soc. (London)A 165 (1938), 372;A 119 (1939), 339; Phil. Mag.25 (1938), 899.
Goodenough J. B. (unpublished research).
Author information
Authors and Affiliations
Additional information
Operated with support from the U.S. Air Force.
Rights and permissions
About this article
Cite this article
Goodenough, J.B. Narrow-band electrons in transition-metal oxides. Czech J Phys 17, 304–336 (1967). https://doi.org/10.1007/BF01691621
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF01691621