Joaquín García and Gloria Subías 2004 J. Phys.: Condens. Matter 16 R145 doi:10.1088/0953-8984/16/7/R01
Joaquín García and Gloria Subías
Show affiliationsThis review puts in doubt the classical description of the Verwey (metal–insulator) transition in magnetite on the basis of the wide set of experiments carried out over the last 60 years. We re-analyse here the most relevant experiments used to study the Verwey transition from the point of view of their degree of agreement with the proposed Fe2+–Fe3+ charge ordering model. We will consider three groups of experimental studies, according to their capability of detecting different ionic species and/or a charge periodicity: (1) Experiments which have been interpreted using the charge ordering model as the starting point though they are not able to demonstrate its validity. This is the case for macroscopic properties such as the electrical resistivity, the heat capacity and the magnetic properties. (2) Experiments which can distinguish different types of Fe ions, such as Mössbauer, nuclear magnetic resonance (NMR) and electronic spectroscopies. However, we show that they are not able to associate them with a specific valence (2+ or 3+ in our case) and, in some cases, they observe more than two different kinds of iron atoms. (3) Diffraction (x-ray, neutron and electron) experiments, which are the most conclusive ones for determining a periodic ordering of different entities. These experiments, instead, point to the lack of ionic charge ordering. We will focus, in particular, on the discussion of the results of some recent x-ray resonant scattering experiments carried out on magnetite that directly prove the lack of ionic charge ordering in such mixed valence oxide. Furthermore, we also reconsider some so-called Verwey-type transition metal oxides in terms of the applicability of the Verwey charge ordering model. We show that a complete charge disproportionation (δ) is not experimentally observed in any of these compounds, the maximum δ being less than 0.5 e−. Regarding the theoretical framework, we will outline some relevant implications for the description of the physics of 3d transition metal oxides of this critical re-examination of the experimental facts on magnetite. Electronic localization should then occur involving more than one transition metal atom, so the definition of ionic d states loses its meaning in mixed valence transition metal oxides.
71.30.+h Metal-insulator transitions and other electronic transitions
Issue 7 (25 February 2004)
Received 15 September 2003, in final form 13 November 2003
Published 6 February 2004
Joaquín García and Gloria Subías 2004 J. Phys.: Condens. Matter 16 R145
Young-Joo Kim et al 2007 Metrologia 44 53
B Franz et al 2009 J. Phys.: Conf. Ser. 190 012200
S.R. Hudson et al 2005 Nucl. Fusion 45 271
K Sadeghipour et al 1994 J. Phys. D: Appl. Phys. 27 1300
X Y Lai et al 2009 New J. Phys. 11 113035
A Narayanasamy et al 1979 J. Phys. F: Met. Phys. 9 2261
J Zoetelief et al 1990 Phys. Med. Biol. 35 1287
Sergey Savel'ev et al 2006 New J. Phys. 8 105
decays in the perturbative QCD approach
Hao Zou et al 2010 J. Phys. G: Nucl. Part. Phys. 37 015002