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Schizophrenic electrons in ruthenium-based oxides †
R. J. Cava
Department of Chemistry, Princeton University, Princeton, NJ 08540, USA
Received 1st March 2004, Accepted 7th April 2004
First published as an Advance Article on the web 26th July 2004
Ruthenium and oxygen form many ternary compounds
in which the Ru 4d states and O 2p states are strongly
hybridized. In some such compounds, this hybridization
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leads to the loss of local magnetic moment character
for the Ru, and in others it does not. The factors that
determine which is the case are often subtle and poorly
understood. The richness of structure types seen in ternary
Ru oxides leads to a corresponding richness in electronic
and magnetic properties. This article briefly describes the
author’s current views on these materials.
1 Introduction
Many of the relationships coupling chemistry, crystal structure,
electronic properties, and magnetic properties in transition
metal oxides remain poorly understood. Unexpected magnetic
and electronic properties frequently surprise the community:
the cuprate superconductors are good examples. This unpre-
dictability of properties is due in large part to the presence of
strong interactions between d electrons – generally too complex
to be treated by the usual theoretical models. But the problem is
much richer than that. Often, the electronic state of a transition
metal oxide is the result of subtle coupling between electronic
and structural degrees of freedom. The 3d-based transition
metal oxides, especially the perovskites, are renowned for
such complexities, supported with decades of observations of
structure–property correlations.
The emergence in the past 5–10 years of correlations of a
similar nature in ruthenium-based oxides was unanticipated. In
more extended orbitals, the 4d valence electrons of Ru are
expected to show fewer tendencies toward localization than
their 3d analogs, and weakened coupling between structural
and electronic degrees of freedom. Unlike 3d oxides, for which
† Based on the presentation given at Dalton Discussion No. 7, 5–7th
July 2004, University of St Andrews, UK.
Robert Cava is a Professor in the Department of Chemistry at
Princeton University. He took that position in 1997 after being
at Bell Laboratories (1979–1997), NIST (1978–1978), and
receiving his PhD in Ceramics from MIT in 1978. He is a member
of the US National Academy of Sciences.
DOI: 10.1039/ b403107e
Robert Cava
This journal is © The Royal Society of Chemistry 2004
electronic–structural coupling can be expected either to be
overtly present or lurking in the background, for the ruthenium
oxides this coupling appears to sometimes be important and
other times not, making them a uniquely interesting class of
compounds. Electrons in ruthenates seem to have an equal
chance of displaying itinerant or localized behavior, often
dependent on subtle structural or chemical influences, thus
motivating the title of this brief review.
Experimental and theoretical research in recent years has
shown that ferromagnetic, antiferromagnetic, and nonmagnetic
states are very close in energy for the ruthenates. This appreci-
ation of the character of the ruthenates was developed by solid
state chemistry groups in the US and Europe, and through
detailed work by experimental and theoretical physicists on one
particular ruthenate, Sr2RuO4, and related perovskite-based
phases. The structural and chemical complexity available in
ruthenates, when combined with this delicate balance between
different magnetic states, offers the potential for observing
many surprising properties. Although the 3d oxides continue to
be the subject of much research, 4d oxides in general have seen
little sophisticated experimental and theoretical study. Thus
they can be considered to be relatively early in their develop-
ment. There is great untapped potential in the ruthenates for
using solid state chemistry to influence the factors that
are important in their determining balance between different
electronic states.
The properties of Sr2RuO4, and how they are related to those
of the Ruddlesden–Popper phases Sr3Ru2O7 and SrRuO3, play
the leading role in illustrating the complexities of the ruthen-
ates. Sr2RuO4 is superconducting, by an exotic microscopic
mechanism, near 1 K.1 Yoshi Maeno and his collaborators have
been the leaders in its characterization, and they have described
its properties in great detail (see, e.g. refs. 2 and 3). The inter-
ested reader is referred to their work to learn about the proper-
ties of that compound. Here, I will paint that material and
related perovskite phases with a broader brush, but using them
as a central part of the argument about the uniqueness of the
ruthenates. I will concentrate mostly on the structures and
properties of non-perovskite ruthenates and will draw primarily
from the work of our group, but will also describe the work
of others.
2 The perovskite and Ruddlesden–Popper phases
The ruthenate perovskites and their layered variants provide an
important testing ground for current ideas in the magnetism of
complex systems, and, in particular, the possible relationships
between ferromagnetism and superconductivity. Sr2RuO4 is
the n = 1, single layer member of the Ruddlesden–Popper
homologous series, Srn⫹1RunO3n⫹1 4–6 (Fig. 1). In this family
n represents the number of layers of corner-shared RuO6
octahedra in each grouping – these n layers are electronically
connected by Ru–O–Ru bonding before the electronic coupling
in the direction perpendicular to the layers is broken up by
O–O–O electronic overlap. As n increases, the proportion of
pure perovskite character increases, and therefore the structures
become more three-dimensional. The evolution of the electro-
nic states from delocalized to ferromagnetic as n increases has
Dalton Trans., 2004, 2979–2987 2979

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Fig. 1 The crystal structures of (a) SrRuO3, (b) CaRuO3, (c) Sr2RuO4
and (d) Sr3Ru2O7. Large grey circles, Sr atoms, large grey circles; Ru
atoms, blue circles; O atoms, small red circles. RuO6 octahedra are
emphasized.
been the subject of considerable study, and illustrates in a single
chemical system the complexities that the ruthenates afford.
Structurally consisting of single layers of corner-shared
RuO6 octahedra, Sr2RuO4 has been found to be electronically
quasi two-dimensional (2D) as well. The magnetic susceptibility
is temperature independent, implying the presence of delocal-
ized electrons, but the Sommerfeld parameter describing the
linear contribution to the specific heat at low temperatures is
approximately 40 mJ mol Ru⫺1 K⫺2,7 indicating an enhanced
mass for the conduction electrons. This degree of mass
enhancement is near the low end of Sommerfeld parameters
displayed by materials with unusual electronic states. Beyond
that, NMR measurements have revealed strong orbital depend-
ent magnetic correlations 8 and inelastic neutron scattering
measurements find incommensurate, antiferromagnetic spin
fluctuations 9 in this compound. A “T = 0 K” paramagnetic to
ferromagnetic phase transition has been observed under
applied pressure.10 These observations suggest that this material
is schizophrenic indeed, being close to ferromagnetic, anti-
ferromagnetic, and superconducting instabilities that compete
for dominance. Surprisingly, substitution of small amounts of
non-magnetic Ti for Ru in Sr2RuO4 has recently been shown to
tip the balance in favor of a magnetically ordered state.11,12 This
also occurs for the CaRuO3 perovskite, as described below, and
may be a unique characteristic of the ruthenates.
Ca2RuO4 has the same basic crystal structure as Sr2RuO4, but
due to the presence of the smaller Ca atom has a substantially
distorted crystal structure, with tilting and rotation of the RuO6
octahedra, making the compound a Mott insulator.13 A further
structural distortion has been found to accompany a transition
to an insulating antiferromagnetically ordered state at low
temperatures 14 – the first example in this review of a common
theme in the ruthenates – that they display subtle and not yet
fully understood coupling between structural and electronic
degrees of freedom. Sr substitution for Ca at a very low level,
2980 Dalton Trans., 2004, 2979–2987
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approximately 10%, relaxes the structural distortions and
induces metallic conductivity, indicating Ca2RuO4 to be barely
in the insulating regime.15
The n = 2 compound, Sr3Ru2O7, was at first the subject of
controversy. In the initial characterization,16 the magnetic
susceptibility was found to show a broad peak around 15 K,
accompanied by Curie–Weiss behavior at high temperatures,
yielding θCW = ⫺15 K and a large local moment of 2.5 µB/Ru. In
a subsequent study,17 using what were called “single crystals” of
Sr3Ru2O7, ferromagnetic (FM) ordering at 104 K was reported.
This result was not supported by neutron diffraction results 18
and was inconsistent with magnetic susceptibility data for
single crystalline Sr3Ru2O7 prepared by the floating-zone
method.19 Although it has never been conclusively established,
it is very likely that the problem with the reports of ferro-
magnetism in this compound are due to the intergrowth of
layers of SrRuO3 or Sr4Ru3O10 in the Sr3Ru2O7 -intergrowth of
foreign stacking sequences within crystals of one dominant
member is not an uncommon phenomenon in Ruddlesden–
Popper phases. Overlooking the possible presence of such
intergrowth phases, and other types of non-uniformity in
“single crystals”, is a common problem in physicists’ work on
complex chemical systems; one that could be remedied
by improved interactions between solid state chemists and
physicists in this field.
The intrinsic properties of Sr3Ru2O7 illustrate the delicate
balance between competing electronic states in the ruthenates.
It possesses what appear to be incommensurate antiferro-
magnetic spin fluctuations,20 and electrical transport measure-
ments have been interpreted in terms of skew scattering by
magnetic fluctuations.21 The Hall coefficient can be decom-
posed into normal and anomalous parts – analogous to the
case of skew scattering in heavy fermion compounds and
ferromagnetic metals. Observations suggest that the magnetic
correlations in Sr3Ru2O7 at ambient pressure undergo a qualita-
tive change as the temperature is lowered. At higher temper-
atures they are dominated by ferromagnetic interactions, but at
low temperatures the system crosses over to antiferromagnetic-
like behavior. Further, a transition to a ferromagnetic state
(a metamagnetic transition) has been observed for fields above
5 T at low temperatures.22 When hydrostatic pressure is applied,
a “T = 0 K” paramagnetic to ferromagnetic quantum phase
transition was also found, similar to that seen in Sr2RuO4,
but with slightly lower critical pressure.19 Thus Sr3Ru2O7
displays nearly the full range of possible electronic states seen in
ruthenates in a single compound.
Ferromagnetism has been reported for Sr4Ru3O10 23 at 104 K,
but given all the problems with intergrowths in this system,
further work is required to verify its intrinsic properties.
However, the reported T c falls nicely in the evolution from
nonmagnetic to ferromagnetic behavior as the number of layers
increases.
The three dimensional perovskite SrRuO3, T c = 160 K, is one
of only a few known ferromagnets among the 4d transition
metal oxides.24 The 3D perovskites themselves provide another
good illustration of the delicate balance involved in determin-
ing electronic states in the ruthenates, as there is an evolution
from ferromagnetism to paramagnetism between SrRuO3 and
CaRuO3. CaRuO3, more structurally distorted than SrRuO3
due to rotation of the RuO6 octahedra, displays Curie–Weiss
magnetic behavior with a significant negative Weiss temper-
ature (⫺200 K) but no magnetic ordering.25 It appears to be one
of the only materials known in which clear Curie–Weiss law
behavior of the susceptibility with negative θCW does not imply
the dominance of antiferromagnetic spin interactions.26
Electronic band structure calculations indicate that SrRuO3 and
CaRuO3 are poised between nearly energetically equivalent
antiferromagnetic and ferromagnetic ground states.27 Although
it is tempting to attribute the differences between these two
materials to the larger deviations of the Ru–O–Ru bond angles

from the ideal 180⬚ in CaRuO3, this has not yet been fully
addressed theoretically for the 4d derived t2g orbitals and
oxygen 2p orbitals involved in this case. Structure and magnet-
ism are clearly deeply connected in the 3D ruthenate perov-
skites, but in a subtle and as yet poorly understood manner.
CaRuO3, cited in the past as a simple paramagnetic material
with antiferromagnetic spin interactions, thus establishing a
baseline for “normal” behavior in this system, is therefore in
actuality quite problematic, and so the evolution of properties
in the ruthenate perovskites is not even simple at the zero-order
level.
Recently, a new context for understanding CaRuO3 has been
proposed, in which it is considered to be a nearly ferromagnetic
metal, rather than a classical Curie–Weiss antiferromagnet.26,27
Small amounts of disorder introduced into CaRuO3 by partial
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substitution of Ru by non-magnetic, isovalent Ti induce
clear ferromagnetic behavior at low temperatures: magnetic
hysteresis loops are observed at 5 K for as little as 2% Ti
substitution.28 This is highly unusual behavior. CaRuO3 itself
therefore seems to be in as yet not well understood electronic
state that can be tipped to ferromagnetism by the introduction
of very small amounts of disorder in the Ru–O network.
In one study 29 on these ruthenate perovskites, a previously
unobserved structure–property effect was uncovered when
comparison was made between the magnetic properties and
structures of isoelectronic CaRuO3, SrRuO3, La0.5Na0.5RuO3,
and their solid solutions. Through chemical doping experi-
ments, a stronger suppression of the ferromagnetism in SrRuO3
through solid solution with La0.5Na0.5RuO3 than through
solid solution with CaRuO3 was found. Through determination
of the structures of the solid solutions in the SrRuO3–
La0.5Na0.5RuO3 case and comparison to the known data for
SrRuO3–CaRuO3, the effects of structural distortion due to
rotations of the RuO6 octahedra were normalized out (Fig. 2).
The results show that solid solutions involving differently
Fig. 2 Comparison of the suppression of the ferromagnetism in
SrRuO3 for the charge-disordered SrRuO3–La0.5Na0.5RuO3 solid
solution and the conventional SrRuO3–CaRuO3 solid solution. Both
systems maintain the 4⫹ oxidation state of the Ru. The data
characterizing the magnetism (saturation magnetization and θCW) have
been plotted for the same degree of structural distortion (Ru–O–Ru
angle) in both systems. It can be seen that the structural distortion (data
labeled “SD”) from the ideal perovskite lattice with 180⬚ Ru–O–Ru
bonds suppresses the ferromagnetism, but that the off-site charge
disorder (data labeled “CD”) introduced by mixing in La3⫹ and Na⫹ on
the Sr2⫹ site has an even stronger effect.
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charged ions on the A-site, – “charge disorder” on the magnet-
ically inactive site – can suppress ferromagnetism, even more
strongly than changing the Ru–O–Ru bond angle.
I have been preaching for some years about the highly
anomalous character of CaRuO3. More detailed investigation
of its properties appears to me to be well warranted. The
perovskite/Ruddlesden–Popper family illustrates fully the range
of unusual electronic states displayed by the ruthenates and
their sensitivity to temperature, pressure, disorder, dimension-
ality, and structural distortion. A full theoretical picture
that integrates all the observed behavior has not yet been
established. Continuing in-depth characterization of materials
in this family will yield ample information to ground such a
picture. For the ruthenates, however, many other structural
families displaying unusual electronic states can also be studied.
Some of those materials are described briefly in the following
sections.
3 Hexagonal perovskites
Although chemically related to the strontium ruthenates,
BaRuO3 displays crystal structures based on a distinctly
different structure type, with no analogs in the Sr–Ru–O or
Ca–Ru–O systems. BaRuO3 has three crystallographic forms,
representatives of the “hexagonal Perovskite” family. Known as
the 9-layer, 6-layer, and 4-layer compounds, they have different
amounts of corner- and face-sharing of RuO6 octahedra – in
turn resulting in different relative contributions of Ru–Ru
and Ru–O–Ru interactions to the electronic structure. The
properties differ considerably, even though the chemical
compositions are identical.
The crystal structures of the two most well characterized
forms of BaRuO3 are shown schematically in Fig. 3.30,31 The
more commonly found 9-layer (9L) form consists of units
of three RuO6 octahedra sharing faces in a partial chain,
facilitating direct Ru–Ru d orbital interactions within the
group, with each of these triple units of octahedra connected to
its neighbors along the hexagonal axis by perovskite-like corner
sharing with nearly 180⬚ Ru–O–Ru bonds. The stacking pattern
repeats after nine octahedra. Similarly, the less common 4-layer
(4L) form consists of units of two octahedra sharing faces
connected to each other by perovskite-type corner sharing, with
a repeating stacking pattern along the hexagonal axis after four
octahedra. Thus the two forms differ in the relative amounts of
direct Ru–Ru and oxygen mediated Ru–O–Ru interactions.
Fig. 3 The crystal structures of (a) 4-layer and (b) 9-layer BaRuO3.
Large blue circles, Ba atoms; grey circles, Ru atoms; small red circles;
O atoms. RuO6 octahedra are emphasized.
Dalton Trans., 2004, 2979–2987 2981

The electrical resistivities of the 4-layer and 9-layer forms of
BaRuO3 have been measured;32,33 representative data are shown
in Fig. 4. For both phases the room temperature resistivities are
in the 200–500 µΩ cm range. The 4-layer phase shows metallic
behavior to low temperatures – residual resistivities on the
order of 100 µΩ cm are seen. The inset to Fig. 4 shows that the
resistivities approximately follow the form ρ = ρ0 ⫹ AT2 at low
temperatures along both characteristic directions. The 9-layer
variant shows at first a metallic resistivity with decreasing
temperature, but then a crossover to a more resistive phase at
low temperatures. The resistivity does not continue to rise
below 10 K in the out-of plane direction, but rather saturates
to a maximum value. Both the 9L and 4L phases appear to be
electronically isotropic.35
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Fig. 4 The resistivities of 9-layer and 4-layer BaRuO3 for the in-plane
(perpendicular to c) and perpendicular-to-plane directions in the
hexagonal crystals, normalized to their 300 K resistivities to facilitate
comparison. Inset – the low-temperature resistivities of the 4-layer
phase plotted vs. T 2.
The magnetic susceptibilities for both phases are small and
paramagnetic, and only weakly temperature dependent, con-
sistent with the full absence of local moment of the Ru ions.
The susceptibilities are due to Pauli paramagnetism of the
conduction electrons. The observed susceptibility values,
∼3–8 × 10⫺4 emu mol-Ru⫺1 Oe, suggest a rather high density of
states at the Fermi level within the standard free-electron
model. For the 4L phase this would correspond to a linear term
in the specific heat (γ) of as much as 50 mJ mol⫺1 K⫺2. The
linear term can be lower if the susceptibility is enhanced by
spin fluctuations. Interestingly, this estimate is consistent with
the prefactor of the T 2 term in the resistivity for this phase,
assuming that it is dominated by electron-electron scatter-
ing.34,35 For the 9-layer phase, the susceptibility is equivalent to
that of the 4-layer phase at 400 K but then decreases smoothly
to approximately half that value by 4.2 K. Following the above
rationale, the average value would correspond to linear term in
the specific heat of as much as 30 mJ mol⫺1 K⫺2. Comparing
this with the directly measured specific heat result,36 one
concludes that the susceptibility for this phase is enhanced by a
factor of 3–4.
The residual resistivities, on the order of 100 µΩ cm, attri-
butable to impurity scattering, are very high, in comparison to
superconducting Sr2RuO4 single crystals (where the residual
resistivity is about 1 µΩ cm 1). The T 2 behavior in resistivity at
low temperatures in the 4L phase indicates Fermi liquid
behavior. In the 9L form, after an initially metallic behavior,
a transition to a more resistive state is observed, apparently
accompanied by the development of a very small ferromagnetic
moment parallel to the chain direction. Further, the properties
2982 Dalton Trans., 2004, 2979–2987
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of the 9L phase appear to be particularly sensitive to the level
of disorder in the sample. This, along with the absence of local
moment behavior, suggests a qualitative similarity to Sr2RuO4.
It would be of interest to see whether very high purity prepar-
ations may show superconductivity. If the electronic states are
indeed analogous in Sr2RuO4 and 4-layer and/or 9-layer
BaRuO3, then one would have to conclude that the layered
structure of the latter compound is not fundamental to its
magnetic and electronic state, in spite of clear implications
that can be drawn from comparison between phases in the
perovskite-based family. Further study of these phases would
be of great interest.
The 6-layer (6L) variant of BaRuO3 has not been character-
ized. However, it is possible to synthesize 6L phases stabilized
by the addition of a third metal element. These compounds
have the hexagonal barium titanate structure type, with pairs of
face-shared RuO6 octahedra interconnected by corner-sharing
MO6 octahedra. This structure leads to a considerable amount
of regular perovskite character, with Ru–O–M–O–Ru angles
near 180⬚. The structure repeats every six layers of octahedra.
These compounds have the general formula Ba3MRu2O9 where
for the transition metals M = at least Mn, Fe, Co, Ni, Cu, and
Zn 37–41 (many other variants with M selected from other
elemental groups are also known): electronically active 3d
elements may therefore be present in addition to the Ru. The
compounds are all semiconductors, and, for the Cu, Ni and Co
analogs, there is a magnetic transition at approximately 100 K.
Unlike pure BaRuO3, then, in these compounds the Ru bears a
local moment. For Ba3CoRu2O9, for example, the ordered
magnetic moments determined 15 K are 2.8 and 1.3 µB for Co
and Ru, respectively.40,41 Comparing the magnetic properties of
these phases with those of BaRuO3 itself, it is seen that the
addition of the transition element (albeit in large proportions)
has induced local moment behavior on the Ru.
Although BaRuO3 itself is a metallic conductor, all of the
members of the M = 3d element Ba3MRu2O9 family are
non-metallic.41 This result is not surprising for M = Zn because
the zinc orbital–oxygen orbital overlap is expected to be poor.
For the other 3d metals, however, this is unexpected, as the
overlap should be better; nonmetallic behavior over a wide
range of electron counts is, however, observed. At room tem-
perature the Ru–Ru distances between face shared octahedra
(∼2.6 Å) are short enough to allow good direct Ru orbital
overlap and sharing of electrons. The 180⬚ Ru–O–M–O–Ru
bonds are expected to have the correct geometry to allow con-
duction through the octahedral site, thus coupling the
ruthenium dimers. This, however, does not seem to occur. The
temperature dependence of the resistivities suggests that the M
atoms in the octahedral sites effectively lead to localization of
the charge carriers and isolation of the Ru dimers, implying
that the energies of the 3d transition metal states are quite
different from those of the Ru.
There is substantially less detailed characterization of the
hexagonal perovskites than of the usual perovskite phases.
Indications are that there are interesting electronic properties to
be uncovered in this structural family with further work.
4 Pyrochlores
Compounds with the pyrochlore structure can be represented
by the general formula A2(B2O6)O⬘ – emphasizing that the
structure consists of a rigid three-dimensional B2O6 network of
corner-sharing BO6 octahedra, with A and O⬘ atoms occupying
interstitial sites. Oxygen vacancy formation, if it occurs, prefers
the interstitial O⬘ site. The chemical variables commonly used
to modify the physical properties of these compounds are
oxygen vacancy content and metal-site substitution.42 The B2O6
array of the pyrochlore structure is shown in Fig. 5.
The electronic properties of the ruthenate pyrochlores are
not comprehensively understood, though they have been of

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Fig. 5 The pyrochlore crystal structure of Bi2Ru2O7. Bi atoms, large
grey circles, Ru atoms, small purple circles, O atoms, small red circles.
RuO6 octahedra are emphasized.
interest for some time.43 Bi2Ru2O7 and Pb2Ru2O6.5 are weakly
metallic, displaying no local moment on Ru and temperature
independent resistivities over a broad temperature range.
Conversely, Y2Ru2O7 and the Ln2Ru2O7 series are insulators,
although formally isostructural and isoelectronic to their
metallic counterparts. Some publications consider the small
Ru–O–Ru bond angle for lanthanide and yttrium pyrochlores
as a possible explanation for their decreased conductivity: 44,45
as the bond angle decreases, orbital overlap will also decrease,
resulting in a narrowed band and decreased mobility. However,
the difference in Ru–O–Ru bond angle between metallic
Bi2Ru2O7 and non-metallic Pr2Ru2O7 is less than 2⬚, making it
unlikely that this is the primary reason for the difference in
properties. It has also been proposed that hybridization of Bi
and Ru states present at the Fermi energy in Bi2Ru2O7 leads to a
wider conduction band relative to pyrochlores with lanthanide
A-site elements.46
The RuO6 coordination polyhedron in Bi2Ru2O7 has been
described as a regular octahedron (symmetry Oh). More
precisely, however, the symmetry is trigonal antiprismatic
(symmetry D3d). There is a compression of the ideal octahedron
along a three-fold axis. The degree of compression can be
measured by the angle (α) between the three-fold symmetry axis
and the Ru–O bond. In an ideal octahedron, α = 54.7⬚, while in
Bi2Ru2O7, α ∼ 58.5. For Ru4⫹, which has four t2g electrons, this
distortion and lowering of symmetry can cause what would be a
partially filled band for a regular octahedron to split into a
completely filled band and an empty band for a triangular
antiprism.42,47
Electronic band structure calculations performed for
Bi2Ru2O7 showed that the ruthenium t2g states are split, in good
agreement with what is expected for D3d symmetry.48 The Fermi
energy (EF) lies at the top of a filled band (eg⬘) of four electrons
per ruthenium, while directly above EF an empty band (a1g) is
found which can accommodate two electrons per ruthenium.
These bands overlap slightly, and the density of states at
the Fermi energy is lowered almost to zero. The Bi2Ru2O7
pyrochlore can therefore be classified as a semi-metal. Similar
band splitting occurs for Y2Ru2O7, Ln2Ru2O7 and others.
The Ru–O–Ru angle between corner-shared octahedra is
120⬚ in Y2Ru2O7 and 133⬚ in Bi2Ru2O7. This difference has
several effects on the electronic structure. The primary effect is
that in Y2Ru2O7, there is a 1 eV gap between the split ‘t2g’
band and the higher energy eg band. In Bi2Ru2O7, where the
Ru–O–Ru angle is increased, the two bands overlap somewhat.
Secondly, the overall band width of calculated ‘t2g’ states for
Bi2Ru2O7 is ∼2 eV, while in Y2Ru2O7 the band width is about
1.5 eV. This narrowing effect would be less pronounced in
Pr2Ru2O7, also an insulator, where the difference in Ru–O–Ru
angle from that in Bi2Ru2O7 is smaller. It is not clear whether
the 25% decrease in band width can cause the insulating prop-
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erties of Y2Ru2O7. In fact, the electronic structure calculations
suggest that Y2Ru2O7 should be weakly metallic, similar to
Bi2Ru2O7. One factor such calculations do not include is
electron–electron correlation. Recently Y2Ir2O7 was found to be
a Mott–Hubbard insulator, which is a direct result of electronic
correlation.49 However, in that pyrochlore, iridium is in d5
electronic configuration, yielding a one electron half-filled a1g
band, expected to maximize the influence of correlations. In
Bi2Ru2O7, ruthenium is d4 with one electron fewer; therefore
electronic correlation should be reduced.
Bi2Ru2O7 is a poor metal, with paramagnetic magnetic
susceptibility, and the experimentally determined density of
states at EF is reported as ∼4 states/eV-Ru.50 We proposed that
the t2g band splitting intrinsic to the D3d Ru-site symmetry leads
to the low value of N(EF) and semi-metallic character for
Bi2Ru2O7. The Fermi level in Bi2Ru2O7 lies in a sharp density of
states valley, and subtle changes such as A-site disorder may
have a dramatic effect on the electronic properties. While the
electronic properties of Bi2Ru2O7 are nicely explained in a
conventional band picture, the electronic properties of Y2Ru2O7
are not. Unlike CaRuO3, Bi2Ru2O7 cannot be made to display
ferromagnetism by small percentages of substitution of foreign
atoms,51 suggesting that ruthenates in the pyrochlore structure
are very far from the kinds of magnetic instabilities and exotic
electronic states that make the perovskite phases so interesting.
Aside from figuring out for certain the cause of the insulating
behavior in the Ln2Ru2O7 variants, the ruthenate pyrochlores
have not yet shown the kind of properties that suggest they are
worthy of continuing detailed study.
5 Hollandites
The tetragonal hollandite crystal structure consists of double
chains of edge sharing RuO6 octahedra running parallel to the
crystallographic c axis (Fig. 6). Alkali or alkaline earth atoms
occupy large tunnels running in the same direction.52 These
tunnels may be occupied in the relative proportion 1 : 6 or 1 : 4,
yielding for example ruthenate hollandites with the formulas
BaRu6O12 and KRu4O8. These have formal Ru oxidation states
of 3.67⫹ and 3.75⫹, respectively. The structure is highly
one-dimensional in character. 1D metals are an important in
contemporary condensed matter physics: electron–electron
interactions in 1D can lead to a breakdown of Fermi liquid
theory. The hollandites provide the opportunity to study these
unusual 1D phenomena in ruthenates.
Fig. 6 The hollandite crystal structure. The double chains of edge
shared RuO6 octahedra are shown. The large one-dimensional tunnels
are also seen. The large “A” ions (grey circles) occupy these tunnels in
different proportions with different periodicities along the RuO2 chain
direction.
Fig. 7(a) shows the temperature dependences of the resistivity
parallel and perpendicular to the ruthenium–oxygen chains in
BaRu6O12.53 The resistivity along the chains is metallic over the
whole temperature range (0.3–300 K), showing slope changes
around 210 and 100 K (Fig. 2(a)). The magnetic susceptibility
χ(T ) exhibits similar features around the same temperatures.53
Interestingly, a semiconducting to metallic crossover in the
a-axis resistivity is seen around 210 K. The high temperature
Dalton Trans., 2004, 2979–2987 2983

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Fig. 7 Temperature dependence of the electrical resistivity with
current flowing parallel (ρc) and perpendicular (ρa) to the Ru–O chain
direction for BaRu6O12.
behavior shows that the electronic system at high temperatures
is effectively 1D. As the temperature is lowered, the interchain
coupling increases, leading to a 1D to 3D crossover in
properties and metallic resistivity perpendicular to the chain
direction at low temperatures
The resistivity of BaRu6O12 is sensitive to disorder.53 The
value of the residual resistivity ratio (RRR), quantifying the
level of disorder, was found to vary from crystal to crystal,
ranging from 11.3 to 2.6 among 50 crystals measured. All sam-
ples measured down to 0.3 K showed a drop in ρ| |(T ) below
2 K. The sharpness and the relative size of the drop, as well as
the slope above the drop, depended sensitively on the “RRR”.
(RRR, the residual resistivity ratio, is the ratio of the resistivity
at 300 K to the resistivity at 4.2 K. Because the low-temperature
resistivity is largely determined by impurity scattering the RRR
is a good measure of sample purity.)
It has been proposed 53 that the observed properties indicate
that there is a quantum phase transition 54 in BaRu6O12. A
slightly increasing resistivity seen in the RRR = 2.6 sample
above the 2-K resistivity drop suggests that a weakly localized
ground state might be present in this material, induced by
disorder. Further, in the high RRR sample, application of a
magnetic field suppresses the resistivity drop, resulting in an
upturn on decreasing temperature. The characteristic temper-
ature below which the resistance shows an upturn increases as
the field increases, showing that the field stabilizes the tendency
toward electron localization. The observed change in resistivity,
tuned by a magnetic field, was proposed to be a true quantum
phase transition between two fundamentally different ground
states – one metallic and the other weakly localized. The
magnetic field induced weakly localized ground state in
BaRu6O12 is unique among ruthenates.
Surprisingly, the electronic behavior of the alkali hollandites,
typified by KRu4O8 and RbRu4O8, is completely different.55
The susceptibilities of KRu4O8 and RbRu4O8 are basically tem-
perature independent, with small magnitudes, on the order of
1 × 10⫺4 emu mol Ru⫺1 Oe⫺1, consistent with temperature
independent Pauli paramagnetism. KRu4O8 and RbRu4O8 are
good metallic conductors, with reasonable RRR, between
40 and 50. Their residual resistivities are very small, on the
order of 3 µΩ cm⫺1 at 4 K – not quite in the range needed to
observe superconductivity in Sr2RuO4 56 but very good. For
KRu4O8, a low-resistivity sample cooled down to 0.3 K showed
no anomalous behavior of any kind, in sharp contrast to the
case of the BaRu6O12 hollandite. Specific heat measurements
revealed that the Sommerfeld parameter γ is approximately the
same for both KRu4O8 and RbRu4O8, given by γ = 3 mJ mol
Ru⫺1 K⫺2. This suggests only minimal enhancement of the
carrier mass compared to the free electron mass, and is con-
siderably lower, for example, than the 40 mJ mol Ru⫺1 K⫺2
found for Sr2RuO4.7 Thus of all the known ruthenates, the
alkali hollandites appear to be the most conventional in
2984 Dalton Trans., 2004, 2979–2987
View Article Online
electronic character. It is not known why there is such a
dramatic difference in properties between the BaRu6O12 and
alkali ruthenate hollandites, but it may be related to the differ-
ent ratio of A ions to RuO2 units: the different A atom
periodicities (and charges) along the tunnels likely impose
different periodic potentials on the Ru–O chains, possibly
influencing the properties. Further work to establish the nature
of the unconventional electronic state of BaRu6O12 would be of
considerable interest.
6 La3Ru3O11 and La4Ru6O19
In all the perovskite-based families, the magnetic and electronic
character derives from the special characteristics of transition
metal–oxygen orbital hybridization. The ruthenates are distinct
from many 3d-based chemical systems, as structure types other
than classical perovskites are relatively straightforward to
synthesize. Two such materials are La4Ru6O19 and La3Ru3O11.
The crystal structures of La4Ru6O19 57 and La3Ru3O11 58 are
derivatives of the cubic KSbO3 structure type, which is known
to compete with perovskites for stability in several chemical
systems. The structure of both compounds contains pairs of
edge-shared RuO6 octahedra, effectively forming Ru2O10
dimers, which are connected to other dimers through corner-
shared oxygen. The structures are shown in Fig. 8(a) and (b).
The result is a 3D Ru–O network. The formal Ru oxidation
state is ⫹4.33. La3Ru3O11 and La4Ru6O19 therefore have an
identical Ru–O network geometry and identical formal Ru
oxidation state. In La4Ru6O19, the Ru–Ru distance across the
shared edge of the octahedra in the dimers is 2.49 Å, smaller
than the shortest Ru–Ru distance in Ru metal (2.65 Å) or that
in RuO2 (3.11 Å), indicating the presence of Ru–Ru bonding. In
La3Ru3O11, in contrast, the Ru–Ru distance in the dimers is very
large, indicating that no metal-metal bonding is present.
Fig. 8 Two crystallographic units cells of (a) La4Ru6O19 and (b)
La3Ru3O11. RuO6 octahedra are shown as shaded polyhedra (with Ru
inside). A virtually identical Ru–O network is seen for each. La and
non-network O are shown by closed and open circles, respectively.
Electronic structure calculations 59 on La3Ru3O11 show a
manifold of delocalized states (broad bands several eV wide) –
similar to those seen in ruthenate perovskites, due to strong
Ru–O orbital hybridization. However, similar calculations for
La4Ru6O19 revealed not only the presence of the usual Ru–O
derived broad bands, but also additional localized electronic
states (narrow bands) near the Fermi energy. Analysis has
shown that the localized states originate from the Ru–Ru bonds
in the dimers in La4Ru6O19. Thus both localized and delocalized
electronic states are expected to be present near the Fermi
energy in this material. The result is a unique compound – with
both localized and delocalized states coming from different
kinds of orbitals derived from the same atoms.
While La3Ru3O11 displays electronic and magnetic behavior
typical of metallic oxides, La4Ru6O19 has a number of highly

unusual electronic properties.60 At room temperature, the resist-
ivity is 2.5 mΩ cm, much larger than the ∼10⫺5 Ω cm typically
observed for RuO2. Below 30 K, a linear T -dependence in
resistivity is observed. Linear resistivity is frequently cited as
one of the characteristics of the cuprate superconductors
(where it persists to much higher temperatures) that show that
they are unconventional materials. Specific heat measurements
revealed that C(T )/T of La4Ru6O19 at H = 0 displays a mini-
mum around 5 K, which rises below 1 K with a ln T behavior
and approaches a value of ∼60 mJ mol Ru⫺1 K⫺2 at low temper-
atures (Fig. 9). The magnetic susceptibility also shows unusual
behavior. These features observed for La4Ru6O19 are quite
similar to those of the intermetallic, heavy Fermion com-
pounds. Both the linear T -dependence resistivity and T ln T
behavior in specific heat were found in CeCu6⫺xAux, the canon-
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ical example of a system close to a “quantum critical point”
between an antiferromagnetically ordered and non-magnetic
ground state.61 Therefore the linear resistivity and T ln T
behavior in specific heat have been taken as primary indications
of non-Fermi liquid behavior in La4Ru6O19, yet another strange
electronic ground state engendered in ruthenates.
Fig. 9 The specific heat data for La4Ru6O19 in various applied fields.
Inset: raw data. Main panel, the data with the Schottky anomaly due
to the nuclear spin component subtracted. The ln T dependence of the
H = 0 data at low temperatures is emphasized with a dashed line.
Metal-metal bonding is known to be present in many 4d and
5d transition metal oxides. The electronic consequences of the
formation of localized states due to the presence of metal-metal
bonding have not been well explored in the context of con-
temporary condensed matter physics. The large size of the
relevant orbitals typically results in wide bands in itinerant 4d
and 5d transition metal oxides, leading to a large kinetic energy.
From the physics point of view, the driving force for the local-
ization of electrons in these compounds must ultimately be
related to the reduction of kinetic energy. The price to pay for
the localization is the increase in repulsive Coulomb inter-
action, which can apparently be minimized through many-body
screening by other conduction electrons originating from
metal–oxygen bonding. The delicate balance between these two
tendencies of electronic motion, localized vs. itinerant, has been
proposed to place the system at a “self-organized” critical state.
Such a unique situation may lead to novel collective
phenomena. La4Ru6O19 clearly falls in the class of the most
exotic of the ruthenates in terms of its electronic properties.
7 La4Ru2O10 62
As a final example, I describe a new layered compound,
La4Ru2O10, which has been found to display an unusual
View Article Online
magnetic phase transition at low temperatures, in which the
magnetic moment of Ru is largely lost. Similar to Sr3Ru2O7,
which has double (100) perovskite planes of RuO6 octahedra,
La4Ru2O10 contains double (110) perovskite planes (Fig. 10).
La4Ru2O10 has two closely related crystal structures: a mono-
clinic structure at high temperature and a triclinic structure at
low temperature. The structural transition between the two
forms at 170 K results in a slight atomic displacement that leads
to an ordered array of long and short O–Ru–O bonds within
the double perovskite planes.
Fig. 10 Comparison of the layered crystal structures of Sr3Ru2O7 and
La4Ru2O10. In the former, the layers of RuO6 octahedra are 100
perovskite layers. In the latter, the layers are of the 110 perovskite type.
The formal valence for Ru in La4Ru2O10 is 4⫹, yielding four
electrons in t2g orbitals. Magnetic susceptibility measurements
reveal Curie–Weiss behavior at temperatures above 170 K, with
θCW = ⫺71 K, and a moment of 2.53 µB, close to that for the
expected S = 1 spin configuration of Ru4⫹. For the low-T phase,
Curie–Weiss behavior was again observed, but with θCW = ⫺23
K, and a much reduced moment of 0.39 µB, corresponding
roughly to an S = 0 spin configuration. A dramatic loss of local
magnetic moment has therefore occurred at the structural phase
transition.
In both crystal structures, even considering crystal field
effects brought on by the low symmetry, band structure calcu-
lations suggest that La4Ru2O10 should be metallic. However,
resistivity measurements showed that both the high-T phase
and low-T phase are insulating. At high temperatures, the
resistivity follows an Arrhenius behavior, ρ(T ) ∼ exp(T 0/T ),
with T 0 values near 1100 K, corresponding to a band gap of
approximately 0.1 eV. Below T = 160–170 K, the Arrhenius law
was not found to describe the temperature dependence well.
The observation of insulating behavior with a well-defined gap
indicates that the simple electron band picture that works well
for some ruthenates is not applicable to La4Ru2O10, most likely
due to the presence of strong Coulomb interactions.
The magnetic transition is coupled to a subtle structural
distortion in which a slight atomic displacement leads to an
ordered array of long and short O–Ru–O bonds (Fig. 11). This
type of magnetic transition–structural transition coupling has
been of considerable interest recently in other classes of
materials, such as the manganate perovskites. La4Ru2O10
appears to be the first clear example of orbital ordering in
ruthenium based oxides, i.e. where energetically degenerate
occupied sub-orbitals order in specific directions in a crystal
structure. La4Ru2O10 displays orbital ordering in 4d t2g orbitals
rather than 3d eg orbitals, as has been observed in other com-
pounds and so is representative of a new class of materials.
Such an “orbital ordering” affect, a topic of considerable
current interest for 3d oxides, is quite surprising to find in a 4d
oxide where the orbitals are expected to be more diffusely
distributed.
Dalton Trans., 2004, 2979–2987 2985

Fig. 11 Comparison of the crystal structures of La4Ru2O10 at
temperatures above (monoclinic) and below (triclinic) the phase
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transition where the magnetic moment on Ru is lost. The initially
equivalent O–Ru–O–Ru–O distances characterizing the bond lengths
within the corner-sharing of the octahedra have differentiated into two
distinct, longer and shorter sets of bond lengths, indicating ordering in
the occupancy of the orbitals within the RuO6 octahedra.
8 Conclusions
Hopefully this review has illustrated that there appear to be a
never-ending variety of unusual magnetic and electronic states
displayed by ruthenium based oxides. Both survey-like and in-
depth studies of their properties often reveal that the properties
are coupled to crystal structure in a manner that although well
explored for 3d metal oxides is not well explored for 4d oxides.
It seems that no matter which rock one looks under, a
schizophrenic electronic state is hiding. The author attributes
this to the highly unusual character of Ru–O bonding and
the diversity of crystal structures and oxidation states possible
for ruthenates. Though these compounds are typically more
difficult to synthesize than well studied 3d compounds, con-
tinuing detailed work would clearly be of great interest. I
believe that they are worth further research investment, and
hope that this review is useful in pointing out why that may be
the case.
Acknowledgements
The author would like to thank the US National Science
foundation, DMR Solid State Chemistry Program, for support
for his research in ruthenium-based oxides. He further would
like to thank his students and collaborators, who contributed
very much to what is described here, in particular Peter
Khalifah, Tao He, Ying Liu, Mary Haas, Job Rijssenbeek, Qing
Huang, J. W. Lynn, Maw Lin Foo, A. P. Ramirez, B. Batlogg,
G. Lawes and Kim Regan.
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