HF1

Charge ordering, charge uctuations and lattice eects in strongly
correlated electron systems

Terutaka Goto{
Graduate School of Science and Technology, Niigata University, Niigata 950-2181,
Japan
and Bruno Lu thi{
Physikalishes Institut, Universita t Frankfurt, Frankfurt D-60054, Germany
[Received 26 April 2002: revision received 2 September 2002; accepted 12 September 2000]
Abstract
Charge uctuation and charge-ordering phenomena in compounds based on
the 3d electrons of transition-metal ions and 4f electrons of rare-earth ions are
reviewed with particular emphasis on the mutual coupling of charge and lattice
degrees of freedom. For the description of charge ordering in inhomogeneously
mixed-valence compounds of localized 3d or 4f-electron systems, we employ
Landaus phenomenological theory for second-order phase transitions. By use
of the group-theoretical method, the charge uctuation mode corresponding to the
active representation for the second-order transition is determined. The localiza-
tion of 3d and 4f electrons makes the valence for the specic ions an integer
number of charge units e in the ordered phases at low temperatures. The elastic
soft mode observed by the ultrasonic method is often a useful indication for the
charge uctuation mode that is frozen below the charge-ordering point T
C
. The
transverse c
44
mode exhibiting a considerable softening in the rare-earth com-
pound Yb
4
As
3
couples to the
5
triplet of the charge uctuation mode, giving rise
to a linear chain of magnetic Yb
3
ions along [111] below T
C
292 K. Magnetite
Fe
3
O
4
and the substitution system Fe
3x
Zn
x
O
4
exhibit softening of the c
44
mode
that couples to the charge uctuation mode, which freezes below the Verwey
transition temperature T
V
124 K. The soft c
66
mode of the transition-metal
compound NaV
2
O
5
gives evidence for a zigzag structure of V
4
ions in the ab
plane below T
C
34 K and is the precursor for the orthorhombicmonoclinic
phase transition. The charge glass compounds of Sm
3
X
4
(X Se or Te) show
ultrasonic dispersion due to thermal hopping of 4f electrons between Sm
2
and
Sm
3
ions. The ln T decrease in elastic constants of Sm
3
X
4
is described in terms of
a two-level system of the 4f-electron tunnelling in the random potential. The
characteristic ultrasonic dispersion for the copper oxide compound
Sr
12
Ca
2
Cu
24
O
41
is also presented. The elastic anomaly associated with the charge
ordering in the hole-doped Mn compounds La
1x
Sr
x
MnO
3
and Pr
1x
Ca
x
MnO
3
with colossal magnetoresistance is discussed. In short, the temperature dependence
of some symmetry elastic constants and the frequency dependence of ultrasonic
attenuation coecients help to characterize the charge-ordering transitions. They
can predict the symmetry of charge orderings of the second-order transition, or
they describe the thermal hopping processes of charge or they can identify a charge
glass.
Advances in Physics, 2003, Vol. 52, No. 2, 67118
Advances in Physics ISSN 00018732 print/ISSN 14606976 online # 2003 Taylor & Francis Ltd
http://www.tandf.co.uk/journals
DOI: 10.1080/0001873021000057114
{ e-mail: goto@phys.sc.niigata-u.ac.jp
{ e-mail: luethi@physik.uni-frankfurt.de
Contents page
1. Introduction 68
2. Theory 72
2.1. Phenomenological theory 72
2.2. Calculation of elastic constants 74
2.3. Madelung energy 76
3. Applications: systems exhibiting charge-order phase transitions 77
3.1. Yb
4
As
3
77
3.1.1. Introduction 77
3.1.2. Elastic constant 77
3.1.3. Charge ordering 79
3.1.4. Yb
4
(As
1x
Sb
x
)
3
84
3.2. Fe
3
O
4
and Fe
3x
Zn
x
O
4
85
3.2.2. Elastic constants 86
3.2.3. Symmetry analysis 89
3.3. NaV
2
O
5
91
3.3.2. Elastic constants 92
3.3.3. Symmetry analysis for charge ordering in NaV
2
O
5
95
3.3.4. Other indications favouring a zigzag structure 96
4. Applications: Systems exhibiting a charge glass state or partial
charge ordering 98
4.1. Sm
3
X
4
98
4.1.1. Glass state in Sm
3
X
4
98
4.1.2. Two-level system in Sm
3
Te
4
100
4.1.3. Possible charge ordering in Eu
3
S
4
101
4.2. Sr
14
Cu
24
O
41
and Sr
12
Ca
2
Cu
24
O
41
104
5. Applications: charge and orbital orderings in colossal-magneto-
resistance materials 106
5.1. La
1x
Sr
x
MnO
3
106
5.1.1. Colossal magnetoresistance and orbital ordering 106
5.1.2. Charge ordering 109
5.2. Pr
1x
Ca
x
MnO
3
and Nd
0.5
Sr
0.5
MnO
3
110
6. Conclusion and outlook 114
Acknowledgements 114
References 115
1. Introduction
We discuss recent developments in the eld of the charge-ordering phenomena
for the transition-metal compounds containing 3d electrons and the rare-earth
compounds with 4f electrons. We focus especially on the phenomena due to the
coupling of the charge uctuation mode to lattice degrees of freedom. The orbital as
well as spin degrees of freedom in the magnetic ions with unlled inner d or f shells
lead to a variety of magnetic eects in the systems. The intersite magnetic coupling
between the magnetic ions with localized d or f electrons can take many dierent
forms such as the exchange interaction, superexchange and RudermanKittel
KasuyaYosida interactions. These magnetic interactions lead to a variety of
ferromagnetic and antiferromagnetic orderings in the system. The orbital degrees
of freedom of the 3d and 4f electrons provide the electric quadrupole moments of
the ions. The intersite interaction of these quadrupole moments gives rise to
ferroquadrupole or antiferroquadrupole ordered phases at low temperatures. The
T. Goto and B. Luthi 68
coupling of the quadrupole moment to the lattice degrees of freedom in particular
leads to many dierent types of structural phase transition. The strain coupling to
quadrupole moments leads to the cooperative JahnTeller eect. Because of this
quadrupolestrain interaction, the ultrasonic measurement of the elastic constants
and attenuation coecients is a unique probe to observe the strain susceptibility for
the 3d- or 4f-electron system. It is generally expected that the electron system with an
orbital degenerate ground state exhibits a softening of the transverse elastic
constants.
The 3d electrons of transition-metal ions and especially the 4f electrons in rare-
earth ions are often localized inside the inner shell of the magnetic ions in the
chemical compounds. In some transition-metal compounds, however, ions with
dierent valences such as Fe
2
and Fe
3
, V
4
and V
5
, Mn
3
and Mn
4
, and
Cu
2
and Cu
3
are coexistent. The rare-earth compounds based on Sm, Eu, Tm and
Yb ions frequently exhibit the mixed-valence state consisting of divalent and
trivalent valences. In the mixed-valence compounds, therefore, one must also
consider the charge degrees of freedom of the 3d or 4f ions in addition to the spin
and orbital degrees of freedom.
To specify this process it is necessary to distinguish between homogeneously
mixed-valence compounds and inhomogeneously mixed-valence compounds. In the
former, there is essentially a single ion property where the magnetic ion hybridizes
with the sea of conduction electrons, causing an exchange of an inner electron with
the conduction band at the Fermi level. In the case of inhomogeneously mixed-
valence compounds, the 3d or 4f electrons can hop between the magnetic ions with
dierent valences, assisted in some cases by the thermally activated motions. Below a
transition temperature there is a distinct charge ordering due to the Coulomb
interaction between the ions of dierent valences.
Typical compounds exhibiting homogeneously mixed-valence phenomena are
rare-earth materials SmS, TmSe, SmB
6
and YbInCu
4
. Reviews dealing with this kind
of valence uctuations have been given by Varma [1], Lawrence et al. [2] and
Wachter [3]. The reduction in ionic radii from divalent R
2
to trivalent R
3
in these
compounds leads to coupling with the breathing lattice mode or the volume strain
B

xx
yy
zz
with full symmetry.
The shrinkage in the lattice volume has been observed across the metal
insulator transition of SmS under pressure, where the insulator phase of SmS
with a black colour dominated by Sm
2
ions changes into the metallic phase with
a golden colour consisting of mostly Sm
3
ions. The negative Poissons ratio
c
12
c
11
c
12
< 0 in Sm
1x
Y
x
S and TmSe and the softening of the bulk
modulus c
B
c
11
2c
12
3 indicate the coupling of the homogeneously mixed-
valence state to the volume strain
B
. The ternary intermetallic compound of
YbInCu
4
and its substitution compounds YbIn
1x
Ag
x
Cu
4
exhibit a valence transi-
tion from the high-temperature metallic phase of mostly Yb
3
ions to the low-
temperature phase, where some of the Yb
3
ions change to Yb
2
ions. It has been
commonly found that the bulk modulus c
B
of YbIn
1x
Ag
x
Cu
4
(x 0, 0.2, 0.25 and
0.3) exhibits a softening around the valence transition temperature [4]. The
hybridization of the localized 4f state of Sm ions to the conduction d-band state
in SmB
6
leads to a narrow band state, and consequently to a high density of states,
with an energy gap 150 K at the Fermi level. The lattice volume of the SmB
6
increases considerably below about 80 K, because electrons populated in the upper
band consisting of Sm
3
-rich states fall into the lower band of Sm
2
-rich states [5, 6].
Charge ordering, charge uctuations and lattice eects 69
As shown in gure 1, the bulk modulus c
B
c
11
2c
12
3 of SmB
6
shows a marked
softening with a rounded minimum around 80 K [7]. It is a common feature in that
the homogeneously mixed-valence state in these compounds couples with the volume
strain
B
with total symmetric character. It has been demonstrated that the
deformation coupling mechanism [8, 9] of the narrow 4f-band state in SmB
6
accounts for the softening of the bulk modulus and the anomalous increase in the
lattice volume at low temperatures. The monotonic increase in the transverse
c
11
c
12
2 and a small dip in the transverse c
44
mode in gure 1 reveals that the
coupling of the homogeneously mixed-valence state to the symmetry-breaking strain
corresponding to the transverse modes has only a secondary eect on the system.
For the inhomogeneous case, one of the famous examples of charge uctuation
phenomena is magnetic Fe
3
O
4
where Fe
2
and Fe
3
ions exhibit charge ordering.
The charge ordering of NaV
2
O
5
due to V
4
and V
5
has recently attracted much
attention because of the contrast to the inorganic one-dimensional spin-Peierls
system (e.g. CuGeO
3
). The charge ordering due to the doped Mn
4
ions in a sea
of Mn
3
ions in the manganese perovskite compounds La
1x
Sr
x
MnO
3
and
Pr
1x
Ca
x
MnO
3
has been investigated intensively, because the charge degrees of
freedom in addition to the spin and orbital degrees of freedom of Mn ions have a
considerable eect on the colossal magnetoresistance (CMR) of the systems. The
Figure 1. Elastic softening of the bulk modulus c
B
of the intermediate-valence compound
SmB
6
together with c
11
c
12
2 and c
44
modes. The minimum around 80 K in c
B
of
SmB
6
indicates the energy gap D 150 K at the Fermi level.
doping of Ca ions into the spin-ladder system of Sr
14
Cu
24
O
41
leads to an enhanced
charge uctuation eect due to Cu
2
and Cu
3
ions.
The rare-earth pnictide Yb
4
As
3
with the cubic anti-Th
3
P
4
structure exhibits
charge ordering, where the magnetic Yb
3
ions align along the body-diagonal [111]
direction in a sea of non-magnetic Yb
2
ions [10]. The linear magnetic chain model
based on Yb
3
ions in Yb
4
As
3
is successfully accounted for by the unusual magnetic
properties resembling a heavy-fermion system [1113]. The rare-earth chalcogenides
Sm
3
X
4
(XS, Se or Te) with the Th
3
P
4
structure shows a charge glass state due
to the random distribution of Sm
2
and Sm
3
ions [14]. This glass transition of
Sm
3
X
4
is in strong contrast with the charge ordering of the isomorphous compound
Eu
3
S
4
[15].
The various kinds of phase transition and the lattice eects in the inhomogen-
eously mixed-valence compounds are the subject of this review. There are by now
about ten compounds exhibiting such eects. In table 1 we summarize the various
physical properties of the inhomogeneously mixed-valence compounds, which will be
presented in the present article. We shall give a phenomenological description of the
charge-ordering phenomenon stressing the aspect of the coupling to the strain
variables with the symmetry-breaking character. The soft elastic constants relating
to symmetry strains can anticipate the symmetry of the charge order in favourable
cases. They can also describe the dynamics of the thermal hopping processes of
charge and characterize the charge glass state. A microscopic description of these
phenomena does not yet exist and we shall discuss only a treatment based on the
Landau phenomenological theory in emphasizing the symmetry properties in the
charge and lattice coupling.
This review is organized as follows. In the next section 2 we shall discuss in
general terms the Landau theory for charge-ordering transitions, especially taking
into consideration the strainorder parameter coupling and the symmetry aspects of
Table 1. The physical properties of the inhomogeneously mixed-valence compounds based on
the transition-metal ions Fe
3
O
4
, NaV
2
O
5
, La
1x
Sr
x
MnO
3
, Pr
1x
Ca
x
MnO
3
and
Sr
14
Cu
24
O
41
and rare-earth ions Yb
4
As
3
, Eu
3
S
4
and Sm
3
Te
4
.
Material
Valence
states
Charge
ordering
T
C
(K)
Elastic
soft
mode
Charge
uctuation
mode
Structural
change
Fe
3
O
4
Fe
3
, Fe
4
124 c
44
T
2
O
7
h
Fd3m !monoclinic
NaV
2
O
5
V
4
, V
5
34 c
66
B
1
D
13
2h
Pmmn !C
7
2v
Pmn2
1
or monoclinic
La
1x
Sr
x
MnO
3
x 0.12
Mn
3
, Mn
4
145 c
11
c
12
2
c
44
? O
h
Pr
1x
Ca
x
MnO
3
x 0.50
Mn
3
, Mn
4
240 c
11
c
12
2
c
44
T
2g
O
h
Sr
14
Cu
24
O
41
Cu
2
, Cu
3
%150 Ultrasonic
dispersion
Yb
4
As
3
Yb
2
, Yb
3
292 c
44
T
2
T
6
d
I
"
443d !C
6
3v
R3c
Eu
3
S
4
Eu
2
, Eu
3
180 c
11
c
12
2 ? E T
6
d
I
"
443d !D
4
Sm
3
X
4
X Se or Te
Sm
2
, Sm
3
Ultrasonic
dispersion
Charge glass
the charge uctuation modes relevant for the phase transtion. A calculation of elastic
constants within the Landau theory will be given. We shall also briey discuss the
Madelung energy elucidating the energetically lowest state. The following section 3
discusses specic examples exhibiting a charge-ordering transition such as Yb
4
As
3
,
Fe
3
O
4
and NaV
2
O
5
. Section 4 deals with compounds exhibiting charge glass states
or incomplete charge ordering. Examples are Sm
3
X
4
(XSe or Te) and substitution
compounds Sr
14x
Ca
x
Cu
24
O
41
. Finally in section 5 we discuss the new exciting eld
of manganese perovskite La
1x
Sr
x
MnO
3
, Pr
1x
Ca
x
MnO
3
, Nd
1x
Sr
x
MnO
3
with the
CMR. We shall present conclusion, outlook and future development in the nal
section 6.
2. Theory
2.1. Phenomenological theory
In order to describe charge ordering in the inhomogeneously mixed-valence
compounds, it is of interest to employ the Landau phenomenological theory for the
second-order phase transition [16]. In the vicinity of the phase transition point, the
Gibbs free energy is expanded in terms of power series of the charge density jx. y. z
consisting of 3d electrons in the transition-metal compounds or 4f electrons in the
rare-earth compounds. The charge density of the electron system across the charge-
ordering point T
C
is explained in terms of two parts as
j j
0
j. 1
Here the rst term j
0
is an invariant part across the transition point. This means that
j
0
has the total symmetric character of
1
A
1g
in both space groups of G
0
for the
prototype phase above T
C
and G
1
for the ordered phase below T
C
. It is expected that
G
1
is a subgroup of G
0
for the second-order transition. The second term j in
equation (1) is the symmetry-breaking part across the charge-ordering transition,
which is expanded with the charge uctuation mode j
. Here
denotes the
irreducible representation with the symmetry-breaking character, being not A
1g
, of
the space group G
0
above T
C
. The irreducible representation of the charge
uctuation mode is the active mode that is a candidate for the frozen mode at the
charge-ordering point T
C
. The frozen mode becomes the total symmetric representa-
tion of G
1
below T
C
. In this case, the symmetry-breaking part j of the charge
density is written in terms of the charge uctuation mode j
multiplied by the
corresponding order parameter Q
as
j
X
. 2
The order parameter changes from Q
0 in the disordered phase above T

C
to a
nite Q
6 0 in the charge-ordered phase below T

C
. At temperatures far below T
C
,
the order parameter Q
approaches unity: Q
!1. In order to elucidate the

mechanism of the charge ordering, it is very important to project out the bases of
the charge uctuation modes by use of the group-theoretical method [17].
The orbits of 3d electrons in the transition-metal ions and especially the 4f
electrons in the rare-earth ions are well screened by the outer shells. The 3d and 4f
electrons, therefore, have a tendency to be localized even in the valence uctuation
compounds. Consequently, the charge uctuation mode is written by the linear sum
of the charge densities j
i
i 1. 2. . . . . N, owing to the localized 3d or 4f electrons at
the i-sites of the valence-uctuating ions. Here, N is the number of the equivalent
sites of the valence-uctuating ions in the unit cell. In the charge ordering
accompanied by an extension of the unit-cell volume, it is necessary to take the
sites over the extended unit cell.
In the disordered phase above T
C
, the electrons associated with the valence-
uctuating ions make correlated motions and in some cases thermally assisted
motions over the potential hill with activation energy E. Because of these motions
the charge uctuation mode provides the fractional charge in units of e at the sites of
the valence-uctuating ions. In the ordered phase at low temperatures, however, only
integer charges in units of e are relevant because of the localization of the 3d or 4f
electrons in the sites. The excitation energy of the charge uctuation modes with
dierent types of charge distribution are determined by the Madelung energy due to
the long-range Coulomb interaction between valence ions. It is expected that the
mode with the lowest energy freezes at the charge-ordering point. However, as will
be shown in the discussion on Sm
3
X
4
(XSe or Te), the frustation eect due to
avoiding the fractional charge at the ion sites may give rise to a glass state instead of
the conventional charge ordering.
In order to elucidate the charge order in the crystal, we must take the charge
uctuation mode consisting of the linear combination of the charge density j
i
at the
site i in the unit cell. We act with the symmetry operations s fR j bg of the space
group G
0
for the high-temperature phase above T
C
on the charge density
j
i
i 1. 2. . . . . N. Here R is a rotational operator and b is a translation vector
operator consisting of fractional size in unit of the Bravais lattice. Because the
j
i
i 1. 2. . . . . N are dened as the charge density at site i, the symmetry
operations s fR j bg transform j
i
i 1. 2. . . . . N in the same way as the atomic
position vector r
i
i 1. 2. . . . . N. When there are N equivalent sites of the valence-
uctuating ions in the unit cell, one obtains the representation matrices D
ij
s with N
dimensions for each individual symmetry operation s fR j bg of the space group
G
0
as
S
j
1
j
2
.
.
.
j
N
2
6
6
6
4
3
7
7
7
5
fR j bg
j
1
j
2
.
.
.
j
N
2
6
6
6
4
3
7
7
7
5
D
ij
s
j
1
j
2
.
.
.
j
N
2
6
6
6
4
3
7
7
7
5
. 3
The character .
cf
s for the charge uctuation modes with dimension N is obtained
by the trace of the representation matrices as
.
cf
s
X
i1.....N
D
ii
s. 4
By use of the character .
cf
s, one can deduce the irreducible representation
consisting of the charge uctuation modes as [17]

q

1
g
X
s
.
cf
s.
s. 5
Here q
is the number of irreducible representations , which is contained in the

charge uctuation modes of the system. g is the number of the operators s fR j bg
of the space group G
0
. .
s is the character of the irreducible representation in G

0
.
The basis for the charge uctuation mode j
of the irreducible representation
is
obtained as
j
P
lm
j
X
i1.....N
C
.i
j
i
. 6
Here j is an appropriate trial function for the charge distribution and C
.i
is a
coecient. The projection operator P
lm
upon the base of the charge uctuation

mode with the representation
is written as
P
lm
g
X
s
D
lm
ss. 7
Here d
is the dimension of the irreducible representation . D

lm
s denotes the lm
element of the representation matrix D
s for the symmetry operator s. Useful

tables for the representation matrices in space groups have been given by Bradley
and Cracknell [18]. Using equations (6) and (7), we can give the various charge
distributions belonging to the irreducible representations. This we shall demonstate
in detail in the sections to follow.
In the discussion of the charge uctuation modes in insulator compounds, we
must take into account the charge neutrality as a constraint for the system. The
uniform charge distribution for each ionic site due to the motions belongs to the total
symmetric representation of
1
A
1g
. The charge uctuation mode consisting of an
anisotropic charge distribution with symmetry-breaking character is a candidate for
the order parameter in the charge-ordered phase. The experimental observation of
soft elastic constants is a protable way for predicting the charge uctuation mode
responsible for the order parameter. We shall make many applications of the
concepts discussed here in sections 35.
2.2. Calculation of elastic constants
The charge uctuation mode may couple with the lattice degrees of freedom. The
investigation by X-ray scattering and neutron scattering is generally important for
the investigation of the lattice eects related to the charge ordering. The ultrasonic
measurement of the elastic constant around the charge-ordering point in particular
provides a strain susceptibility for the charge uctuation mode characterized at the
Brillouin zone centre point with q 0. The concept of the strain susceptibility will
be discussed below.
The ultrasonic wave induces the elastic strain with various kinds of symmetry. In
the case of a cubic crystal class, the longitudinal c
11
mode propagating along the
[001] direction induces the elastic strain
zz
, which consists of the volume strain
B

xx
yy
zz
with total symmetry
1
A
1g
and the tetragonal strain
u
2
zz
xx
yy
3
p
with
3
E
g
symmetry. The transverse c
11
c
12
2 mode
propagating along the [110] direction with the polarization vector parallel to the
"
1110 direction induces the orthorhombic strain
v

xx
yy
with
3
E
g
symmetry.
The elastic strain
xy
with
5
T
2g
symmetry is induced by the transverse c
44
mode
propagating along the [100] direction with polarization of [010]. A tiny devation
from the orthogonal xy axes to the tilted axes with the angle p2 20 leads to the
elastic strain
xy
sin 0.
The elastic constants of some transverse ultrasonic modes in the charge
uctuation compounds of Yb
4
As
3
, Fe
3
O
4
and NaV
2
O
5
show considerable softening
around the charge-ordering point. In these cases, it is expected that the elastic strain
induced by the transverse ultrasonic wave couples to the charge uctuation

modes in the compounds. In order to explain lattice eects associated with the
charge ordering, it is necessary to take into account the strainorder parameter
coupling in a framework of the Landau phenomenological theory. The free energy of
the system is expanded in terms of the power series of the order parameter Q
as
F
order
F
0
1
2
c
X
Q
2
1
4
u
X
Q
4
. 8
The coecient c c
0
T Y in the second-order term of equation (8) is propor-
tional to the reciprocal charge susceptibility for the charge uctuation mode of j
.
Here Y means the critical temperature for the charge-ordered system. The higher-
order terms in equation (8), usually the even-order terms, are necessary for the
stability of the system. Concerning the lattice part, we need the elastic energy, for
example for cubic symmetry, as
F
lattice

1
2
X
c
0
1
2
c
0
11
2c
0
12
3

2
B
1
2
c
0
11
c
0
12
2

2
u
2
v
1
2
c
0
44
2
yz
2
zx
2
xy
. 9
For the description of the elastic properties of the system, the interaction part
between the order parameter and the strains is necessary. In a cubic crystal class, the
free energy for the interaction term of the bilinear coupling is described as
F
bl

X
3
Q
u
u
Q
v
v
g
5
Q
yz
yz
Q
zx
zx
Q
xy
xy
. 10
Here g
is a coupling constant between the order parameter Q
for the charge

uctuation mode of j
and the elastic strain
. For the description of the

temperature dependence of the elastic constant, we treat the total free energy of
the system as
F
total
F
order
F
lattice
F
bl
. 11
For the equilibrium conditions for the total free energy of the system, we need
0F
total
0Q
cQ
uQ
3
0.
0F
total
0
c
0
0.
9
>
>
>
=
>
>
>
;
12
Taking into account the equation dQ
c 3uQ
2
, we obtain the
renormalized elastic energy of the systems as
F
ren

1
2
X
. 13
For the analysis of the elastic softening above the charge-ordering point T T
0
c
, we
obtain the temperature dependence of the elastic constant from equation (12) as
c

0
2
F
total
0
2
c
0
dQ

c
0
g
2
c
0
T Y
c
0
T T
0
c
T Y

. 14
Here T
0
c
Yg
2
c
0
c
0
is the transition temperature with c
!0 in the presence
of strain interaction. Furthermore, in the case of this bilinear coupling, the structural
change due to the spontaneous strain h
i g
c
0
hQ
i 6 0 is also expected
below the charge-ordering point T
C
. In the following section we present examples of
charge ordering in Yb
4
As
3
, Fe
3
O
4
and NaV
2
O
5
.
The resonant X-ray absorption due to the electronic transition in the second-
order processes among the orbital states has recently been established as a probe
of charge ordering at the superlattice point with q 6 0 [19]. In this case the
quadratic coupling is dominated for the appropriate elastic strain
in the lowest
order as
F
bq
hQ
2
. 15
In order to ensure that the free energy of equation (15) is totally symmetric, one must
project out the second-order polynomials of Q
2
for the bases with the same

symmetry as the elastic strain
. In this process, group-theoretical techniques are

needed. This latter quadratic coupling applies to the cases where the strainorder
parameter coupling is not the primary interaction.
In this case of quadratic coupling, we obtain analogously dQ

2hc 3uQ
2
p
. This leads for the elastic constants to the following:
T T
C
: c c
0
.
T < T
C
: c c
0
2h
2
u
.
9
>
=
>
;
16
We shall treat such a case in the following sections. An extension of the theory to
several order parameters or order parameter components has been given by
Slonczewski and Thomas [20].
2.3. Madelung energy
The group-theoretical analysis shows the symmetry of the charge uctuation
mode and does not provide the Coulomb energy for the charge distribution of the
irreducible representations. It is clear that the Coulomb interactions should take an
important part in considering charge ordering in materials. For this, a Coulomb
lattice gas model is used where each of the mixed-valence ions at a given lattice site
takes a denite charge. The Madelung energy E
M
for the various charge distributions
is calculated by the Ewald method in which the long-range character of the Coulomb
interaction is properly handled. At nite temperatures, the Madelung energy is
averaged over the Boltzmann distributions of the mixed-valence ions on equivalent
lattice sites. A Monte Carlo method is useful for sampling the huge numbers of the
charge conguration at a give temperature [21]. The hybridization eects of 4f or 3d
electrons of mixed-valence cations to surrounding p or d states in anions are
expected to aect appreciably the Madelung energy. Nevertheless the long-range
Coulomb interaction is apparently of importance for manifestation of complemen-
tary behaviour of a charge ordering in Yb
4
As
3
, treated in section 3.1 and a charge
glass state in Sm
3
Te
4
, discussed in section 4.1.
3. Applications: systems exhibiting charge-order phase transitions
In this section we discuss compounds that exhibit charge-order phase transitions
and in particular we show the results for the rare-earth compounds Yb
4
As
3
and
Yb
4
(As
1x
Sb
x
)
3
, for the well-known substances Fe
3
O
4
and Fe
3x
Zn
x
O
4
and for the
recently discovered transition-metal compound NaV
2
O
5
.
3.1. Yb
4
As
3
3.1.1. Introduction
The rare-earth pnictide Yb
4
As
3
with the cubic anti-Th
3
P
4
structure attracts much
attention because the charge ordering of the 4f electrons between valence-uctuating
ions Yb
2
and Yb
3
provides a stage for the one-dimensional magnetic chains at low
temperatures. It has been reported that Yb
4
As
3
exhibits many peculiar low-
temperature properties, a large specic-heat linear T coecient, a plateau of the
magnetic susceptibility and a T
2
dependence of the resistivity [10]. These properties
had initially been thought to result from the low-carrier Kondo eect. The extremely
low carrier density of about 0.1% per Yb ion, however, is not enough to screen the
localized moments of the 4f electrons by the Kondo eect. The inelastic neutron
scattering of Yb
4
As
3
reveals the one-dimensional excitation, which is described by
the model of the Heisenberg interaction with S
1
2
[13]. The low-temperature
properties of Yb
4
As
3
are now explained as a character of one-dimensional magnetic
chains of Yb
3
ions with the Heisenberg-type exchange interaction [11]. Further-
more, the one-dimensional model taking into account the DzyaloshinskyMoriya
interaction due to lack of the inversion symmetry of the crystal structure in Yb
4
As
3
successfully explained the anisotropic behaviour of the magnetic susceptibility
parallel and perpendicular to the linear chains [22, 23]. The origin of the low carriers
of Yb
4
As
3
, however, is still an open problem. A recent review on the physics of
Yb
4
As
3
has been given by Schmidt et al. [24].
3.1.2. Elastic constant
The X-ray scattering and neutron scattering experiments on Yb
4
As
3
show the
structural change associated with the charge ordering. The crystal structure
deformation in Yb
4
As
3
from the cubic class to the trigonal class with the angle
c u 90.748 is accompanied by charge ordering at T
C
292 K [25]. The two
ions Yb
2
and Yb
3
of dierent valences coexist in the population ratio
NYb
2
: NYb
3
3 : 1 under the constraint of charge neutrality in the system.
A very low carrier concentration of about 0.1% per Yb ion in Yb
4
As
3
is consistent
with the assumption of charge neutrality. The charge uctuation motions of Yb
2
and Yb
3
ions are thermally excited in the high-temperature region. One of four
body-diagonal directions in the cubic crystal shrinks considerably below the charge-
ordering point. The specic heat, resistivity and lattice constant at T
C
292 K
indicate the rst-order phase transition of charge ordering. It is noted that
Yb
3
(f
13
: J
7
2
, L 3, S
1
2
) is a magnetic ion, while Yb
2
(f
14
: J 0, L 0,
S 0) is a non-magnetic ion. The polarized neutron scattering experiment in applied
magnetic elds detected clearly a linear chain of the Yb
3
ions with induced
magnetic moment aligned along the body-diagonal [111] direction [12]. Other
body-diagonal directions of [
"
1111], [1
"
111] and [11
"
11] are occupied by the non-magnetic
Yb
2
ions.
The elastic constants of Yb
4
As
3
have been measured by the ultrasonic method
[26]. The transverse c
44
mode of Yb
4
As
3
in gure 2 exhibits a softening of about
20% above the charge-ordering point at T
C
292 K, while the other transverse
c
11
c
12
2 mode and the longitudinal c
11
mode show step-like anomalies at T
C
.
These results suggest that the elastic strains
yz
.
zx
and
xy
of the c
44
mode with
5
T
2
symmetry couple to the charge uctuation modes with the same symmetry. In
section 3.1.3, we project out the charge uctuation mode responsible for charge
ordering and discuss the elastic anomalies based on the Landau phenomenological
theory. The anomalies for c
11
, (c
11
c
12
2 and c
B
show positive steps at T
C
contrary to equation (16), probably because of the rst-order nature of the
transition.
Figure 2. Elastic constants of the inhomogeneously mixed-valence compound Yb
4
As
3
. The
softening of the transverse c
44
mode above the charge ordering point T
C
292 K is
tted by the formula c
44
c
0
44
T T
0
c
T Y with T
0
c
247 K and Y 234 K.
Note the positive steps at T
C
for other elastic modes.
3.1.3. Charge ordering
There are two molecules in a unit cell of the Bravais lattice of Yb
4
As
3
, where
Yb
2
and Yb
3
ions may occupy the eight equivalent sites. As shown in the
conventional unit cell (containing four molecules) of gure 3, we settle
j
i
j
i
x. y. z located at the sites of the Yb ions. Here we write the coordinates
x. y. z in units of the lattice constant a. The Bravais lattice is dened by the
following vectors:
1
2
a. a. a,
1
2
a. a. a and
1
2
a. a. a:
Yb1 : j
1
j
1
u. u. u.
Yb2 : j
2
j
2
u. u. u
1
2
.
Yb3 : j
3
j
3
u
1
2
. u. u.
Yb4 : j
4
j
4
u. u
1
2
. u.
Yb5 : j
5
j
5
u
1
4
. u
1
4
. u
1
4
.
Yb6 : j
5
j
5
u
1
4
. u
1
4
. u
3
4
.
Yb7 : j
7
j
7
u
1
4
. u
3
4
. u
1
4
.
Yb8 : j
8
j
8
u
3
4
. u
1
4
. u
1
4
.
9
>
>
>
>
>
>
>
>
>
>
>
>
>
>
>
>
>
=
>
>
>
>
>
>
>
>
>
>
>
>
>
>
>
>
>
;
17
The u parameter of Yb
4
As
3
is 0.069. Because of the bcc symmetry of the present
crystal, the other eight equivalent Yb sites, described by Yb(i)*, in the conventional
unit cell of gure 3 are obtained by the pure translation operation fE j
1
2
.
1
2
.
1
2
g of the
Figure 3. The Yb sites (Yb(1), Yb(2). . . . . Yb(8)) and As sites (As(1), As(2). . . . . As(6))
responsible for charge uctuation modes in Yb
4
As
3
. The four molecules of Yb
4
As
3
are involved in the conventional unit cell in the Figure. Yb(i)* and As(i)* in the
gure are obtained by the translation fE j
1
2
.
1
2
.
1
2
g on Yb(i) and As(i) respectively.
charge densities j
i
i 1. 2. . . . . 8 of equation (17). The 24 symmetry operators
s fR j bg of the space group T
6
d
I
"
443d, which are found in the International Tables
for Crystallography [27, p. 661], are listed in table 2. In table 3 we give the symmetry
elements of the low-temperature charge-ordered phase C
6
3v
R3c below T
C
.
In order to examine the character of the charge uctuation modes of Yb
4
As
3
, the
24 symmetry operators of the space group T
6
d
act on the charge densities
j
i
i 1. 2. . . . . 8. The trace of the representation matrix with eight dimensions in
equation (4) gives the character .
cf
s for the charge density as shown in table 4.
Using the character .
s of the irreducible representations for the space group T

6
d
,
we reduce the charge density to the direct sum of the irreducible representations as
A
1
1d A
2
1d T
1
3d T
2
3d. Here d means the dimension of the representa-
Table 2. The 24 symmetry operators for space group T
6
d
I
"
443d of Yb
4
As
3
with the anti-Th
3
P
4
structure.
The translation vector is presented in units of
the lattice vector for the conventional unit cell in
gure 3. The same operators can be taken for the
compounds of Sm
3
X
4
(XS, Se, or Te) with the
Th
3
P
4
structure with the space group T
6
d
(discussed in section 4).
Symmetry operators of T
6
d
fE j 0. 0. 0g fS
4x
j
3
4
.
3
4
.
1
4
g
fC
2x
j
1
2
.
1
2
. 0g fS
4z
j
3
4
.
3
4
.
1
4
g
fC
2z
j
1
2
. 0.
1
2
g fS
4y
j
3
4
.
1
4
.
3
4
g
fC
2y
j 0.
1
2
.
1
2
g fS
4x
j
1
4
.
3
4
.
3
4
g
fC
31
j 0. 0. 0g fS
4z
j
3
4
.
1
4
.
3
4
g
fC
31
j 0. 0. 0g fS
4y
j
1
4
.
3
4
.
3
4
g
fC
33
j 0.
1
2
.
1
2
g fo
da
j
1
4
.
3
4
.
3
4
g
fC
34
j
1
2
. 0.
1
2
g fo
db
j
1
4
.
1
4
.
1
4
g
fC
32
j
1
2
.
1
2
. 0g fo
df
j
1
4
.
1
4
.
1
4
g
fC
33
j
1
2
. 0.
1
2
g fo
dd
j
3
4
.
1
4
.
3
4
g
fC
32
j 0.
1
2
.
1
2
g fo
dc
j
3
4
.
3
4
.
1
4
g
fC
34
j
1
2
.
1
2
. 0g fo
de
j
1
4
.
1
4
.
1
4
g
Table 3. The six symmetry operators of C
6
3v
R3c in the
charge-ordered phase of Yb
4
As
3
with the trigonal
axis along the body-diagonal [111] direction of the
host cubic crystal. Here the translation vectors are
described in units of half for the lattice constants
in the high-temperature phase of T
6
d
in gure 3.
Symmetry operators of C
6
3v
fE j 0. 0. 0g
fC
31
j 0. 0. 0g
fC
31
j 0. 0. 0g
fo
db
j
1
2
.
1
2
.
1
2
g
fo
df
j
1
2
.
1
2
.
1
2
g
fo
de
j
1
2
.
1
2
.
1
2
g
tion. The charge uctuation mode j
of the irreducible representations is obtained

by the projection operator of equation (7). We show the charge uctuation mode j
consisting of the linear combinations of the charge densities j

i
i 1. 2. . . . . 8
located at the Yb ion sites in table 5. For convenience we also list the elastic strains
for the appropriate bases.

The total symmetric mode j
A
1
j
1
j
2
j
3
j
4
j
5
j
6
j
7
j
8
in
table 5 corresponds to the uniform distribution of Yb
3
and Yb
2
ions in
space. With the constraint of charge neutrality in Yb
4
As
3
in the existence ratio
NYb
2
: NYb
3
3 : 1, the j
A
1
mode possesses the mean valence of 2.25e for
each Yb site in the unit cell. The charge uctuation modes of j
A
2
, j
T
1
and j
T
2
with
the symmetry-breaking character represent the anisotropic charge distribution of 4f
electrons at Yb sites in the unit cell. It is noticeable that the charge uctuation mode
with T
2
symmetry couples to the elastic strain
yz
.
zx
.
xy
associated with the soft c
44
mode in Yb
4
As
3
in gure 2. This ultrasonic result suggests that the charge
uctuation mode of j
T
2
in table 5 freezes at the charge-ordering point T
C
of Yb
4
As
3
.
The charge density j of equation (2) responsible for the charge ordering in Yb
4
As
3
is written as
Table 4. Character table for the charge uctuation modes of Yb ions in Yb
4
As
3
with the
space group T
6
d
I
"
443d. Here .
s is the character of the irreducible representation.

.
cf
s is the character of the charge uctuation mode of Yb
4
As
3
obtained from
equation (4).
Character E 6IC
4
3C
2
6o
d
8C
3
Bases
.
A
1
s 1 1 1 1 1 x
2
y
2
z
2
.
A
2
s 1 71 1 71 1
.
T
1
s 3 1 71 71 0
.
T
2
s 3 71 71 1 0 yz. zx. xy
.
cf
s 8 0 0 0 2
Table 5. The charge uctuation mode j
of the irreducible representation in Yb

4
As
3
. Yb
4
As
3
has the anti-Th
3
P
4
structure of the space group symmetry T
6
d
I
"
443d. Here
j
i
i 1. 2. . . . . 8 denotes the charge density located at the Yb-ion sites in the unit
cell of Yb
4
As
3
in gure 3. The elastic strain
is also shown.
Symmetry Charge uctuation mode j
Elastic strain
1
A
1
j
A
1
j
1
j
2
j
3
j
4
j
5
j
6
j
7
j
8

B

xx
yy
zz
2
A
2
j
A
2
j
1
j
2
j
3
j
4
j
5
j
6
j
7
j
8
3
E
u
2
zz
xx
yy
3
p
v

xx
yy
4
T
1
j
T
1
.x
j
1
j
2
j
3
j
4
j
5
j
6
j
7
j
8
j
T
1
.y
j
1
j
2
j
3
j
4
j
5
j
6
j
7
j
8
j
T
1
.z
j
1
j
2
j
3
j
4
j
5
j
6
j
7
j
8
5
T
2
j
T
2
.yz
j
1
j
2
j
3
j
4
j
5
j
6
j
7
j
8
j
T
2
.zx
j
1
j
2
j
3
j
4
j
5
j
6
j
7
j
8
j
T
2
.xy
j
1
j
2
j
3
j
4
j
5
j
6
j
7
j
8
yz
yx
xy
j
X
Q
T
2
.
j
T
2
.
Q
yz
j
T
2
.yz
Q
zx
j
T
2
.zx
Q
xy
j
T
2
.xy
. 18
The ultrasonic [26] and the neutron scattering [12] experiments show that the charge
uctuation mode j
T
2
.yz
. j
T
2
.zx
. j
T
2
.xy
in gure 4 are the ground state of the system,
and the other modes j
A
1
. j
A
2
and j
T
1
are available for excited states.
Concerning the charge distribution in j
T
2
.yz
, for instance, the fractional valence of
2.5e due to the thermally excited motion of 4f holes is expected for Yb(1), Yb(2),
Yb(5) and Yb(7) sites, while the integer valence of 2.0e is expected for Yb(3),
Yb(4), Yb(6) and Yb(8) sites. The fractional valence of Yb ions is only available for
the correlated thermal uctuating motion at high temperatures. However, the integer
valence at Yb sites is realized in the ordered phase far below T
C
, where the thermally
activated motions of the localized 4f electrons die out completely.
There are three possible phases for the charge-ordered state:
(i) Q
yz
6 0, Q
zx
Q
xy
0;
(ii) Q
yz
Q
zx
6 0, Q
xy
0;
(iii) Q
yz
Q
zx
Q
xy
6 0.
Case (iii) is realized for the charge-ordered phase below T
C
292 K of Yb
4
As
3
.
In the low-temperature limit T !0 the order parameters approach unity: Q
yz

Q
zx
Q
xy
!1. The charge density of equation (18) is reduced to
j
order
j
T
2
.yz
j
T
2
.zx
j
T
2
.xy
3j
1
j
2
j
3
j
4
3j
5
j
6
j
7
j
8
. 19
We present the charge distribution j
order
of equation (19) in gure 5. j
order
consists of 3e valence of a 4f hole at Yb(1) and Yb(5) sites located on the body-
diagonal direction and 2e valence of the closed shell at Yb(2), Yb(3), Yb(4), Yb(6),
Yb(7) and Yb(8) sites. However, the ordered phases of cases (i) and (ii) lead to the
fractional valence of Yb ions. It is naturally expected that the localized electrons
favour case (iii) with the integer valence preventing the charge-ordered state for the
cases (i) and (ii) with fractional valence. The charge ordering of gure 5 in Yb
4
As
3
Figure 4. The charge uctuation mode with
5
symmetry of Yb
4
As
3
. The fractional charge
2.5e means the thermal population probability of the 4f electrons. The simultaneous
freezing of the
5
T
2
triplet modes j
T
2
.yz
. j
T
2
.zx
. j
T
2
.xy
gives rise to charge ordering of
a linear Yb
3
chain along the [111] direction in gure 5.
gives rise to a linear chain of magnetic Yb
3
ions along the [111] direction in a sea of
non-magnetic Yb
2
ions.
The charge uctuation mode j
T
2
.yz
. j
T
2
.zx
. j
T
2
.xy
with the T
2
symmetry couples
with the elastic strain
yz
.
zx
.
xy
with the same symmetry associated with the
transverse c
44
mode. Following equation (20), the total free energy describing the
charge ordering of Yb
4
As
3
is given as
F
total
F
order
F
lattice
F
bl
F
0
c
2
Q
2
yz
Q
2
zx
Q
2
xy

c
3
Q
yz
Q
zx
Q
xy
u
4
Q
4
yz
Q
4
zx
Q
4
xy
3
5
Q
2
yz
Q
2
zx
Q
2
xy
1
2
c
0
44
2
yz
2
zx
2
xy
g
5
Q
yz
yz
Q
zx
zx
Q
xy
xy
. 20
The coecient c of the second-order power passes through zero at a characteristic
temperature Y as c c
0
T Y. The third-order term c3Q
yz
Q
zx
Q
xy
gives rise to
the rst-order character of the present phase transition with Q
yz
Q
zx
Q
xy
6 0.
The coecient u of the fourth-order term is chosen to be positive for the stability
condition of the system. The bilinear coupling term F
bl
g
5
Q
yz
yz
Q
zx
zx
Q
xy
xy
leads to the softening of the elastic constant c
44
(see also equation (14)):
c
44
c
0
44
T T
0
c
T Y
. 21
Here the critical temperature T
0
c
Yg
2
c
0
c
0
44
corresponds to the elastic
instability point with c
44
!0 for the second-order structural transition. The elastic
softening of c
44
in Yb
4
As
3
above T
C
in gure 2 is tted with equation (21) with the
parameters T
0
c
247 K and Y 234 K. The dierence between the two character-
istic temperatures g
2
c
0
c
0
44
T
0
c
Y corresponds to the energy gain for the
intersite interaction mediated by the lattice degree of freedom.
Figure 5. A linear chain of the Yb
3
ions along the body-diagonal [111] direction below
the charge-ordering point T
C
292 K of Yb
4
As
3
. This ordered state j
order

j
T
2
.yz
j
T
2
.zx
j
T
2
.xy
results from the simultaneous ordering Q
yz
Q
zx
Q
xy
6 0
corresponding to the charge uctuation modes in gure 4.
The spontaneous lattice distortion from the cubic structure with the lattice angle
p2 to the trigonal structure with a lattice angle c u p2 20 below T
C
in
Yb
4
As
3
is described as
ij
g
5
Q
ij
c
0
44
sin 0 (see also section 2.1). The discontin-
uous change in the lattice angle from c 908 to c 90.748 0 0.378 around T
C
of
Yb
4
As
3
[25] means that there is the spontaneous strain
yz

zx

xy
6.46 10
3
below T
C
. The simultaneous condensation Q
yz
Q
zx
Q
xy
6 0 of the charge
uctuation mode of the T
2
triplet in gure 4 gives rise to the linear chain of the
magnetic Yb
3
ions along the [111] direction in gure 5. The structural change from
the cubic T
6
d
to the trigonal lattice C
6
3v
is consistent with the experimental results [10].
The symmetry operators for the charge-ordered phase of the space group C
6
3v
with the principal axis of [111] are listed in table 3. It should be noted that there
are four possible structures with the principal axes along the body-diagonal [111],
[
"
1111], [1
"
111] and [11
"
11] directions below T
C
. The uniaxial stress on the surfaces
perpendicular to one of the four body-diagonal axes, for example [111], produces
the monodomain structure with the magnetic linear chain of Yb
3
along the [111]
direction below T
C
[12].
The Landau theory based on the group-theoretical analysis successfully explains
the experimentally observed fact of the charge ordering of Yb
3
ions along one of
the four body-diagonal directions. Lorenz [28] has already explored charge ordering
in the anti-Th
3
P
4
structure in conning the primary unit cell to two molecules. The
Lorenz state with the lowest Madelung energy consists of the Yb
3
ions located at
the third-neighbour sites. The symmetry operation reveals that the Lorenz state
consists of the
4
T
1
charge uctuation mode in table 5 [26]. This means that the
Lorenz state is not able to couple to the soft c
44
mode. Iyetomi et al. [21] have
proceeded to a larger conguration space, the conventional unit cell with four
molecules and even a supercell with 32 molecules. From the Madelung energy
calculation, they obtained a new lowest state in addition to the Lorenz state located
at 300 K above and the Yb
3
linear-chain state located at 600 K further above. In the
lowest state of the Madelung energy estimate, there are three dierent kinds of Yb
chain along the [111] direction: chains of Yb
2
alone, chains of Yb
3
and Yb
2
arranged alternately and chains in which Yb
3
are arranged in every three sites. This
lowest-state-charge conguration anticipated by the Madulung energy diers
completely from the Yb
3
linear-chain state realized below T
C
in Yb
4
As
3
. The
hybridization eects of the 4f electrons of Yb to the p electrons of As may gain
energy of more than 600 K for the Yb
3
linear-chain state. The one-dimensional
band model by Fulde et al. [11] is a possible way for this to be achieved.
3.1.4. Yb
4
(As
1x
Sb
x
)
3
The elastic properties of the substituted system Yb
4
(As
1x
Sb
x
)
3
are also
interesting, because one can examine charge ordering in the system with random
potential and doped carriers [29]. In the case of a low-doped compound of x 0.12,
the transverse c
44
mode exhibits a pronounced softening of 34%, which is twice the
amount of softening of c
44
in pure Yb
4
As
3
. The softening of c
44
in a compound with
x 0.12 is also described by equation (21). This means that, even in the doped
system with x 0.12, the charge ordering to the linear chain of Yb
3
ions along the
[111] direction is now close to the second-order transition. In the higher-doped
compounds with x 0.24 and 0.29, however, the softening of the shear c
44
mode is
weaker, and the longitudinal c
11
mode or the bulk modulus c
B
shows a rounded
minimum around the charge-ordering point. This result suggests that the random-
ness and the carriers in the highly doped compounds tend to favour the charge glass
state instead of charge ordering with a symmetry-breaking character in analogy to
Sm
3
Se
4
and Sm
3
Te
4
. The ultrasonic attenuation c
11
of the longitudinal c
11
mode of
x 0.29 in gure 6 exhibits a frequency dependence obeying an Arrhenius-type
dispersion around the charge-ordering point. The ultrasonic dispersion in gure 6 is
analysed using equations (22 a) and (22 b) in section 4.1.1. The peak of the
attenuation coecient c
11
indicates that the characteristic time 2p.
s
of the
ultrasonic wave coincides with the relaxation time t of the system. The relaxation
time t of the compound with x 0.29 in gure 7 obeys the thermal activation-type
temperature dependence t t
0
exp Ek
B
T with an activation energy E 0.038 eV
and t
0
4.5 10
12
s. It is expected that the relaxation time of the compound with
x 0.29 is close to that of pure Yb
4
As
3
. At the T
C
292 K corresponding to the
charge-ordering point of pure Yb
4
As
3
, the relaxation time of the compound with
x 0.29 in gure 7 is t 2 10
11
s, which is a reasonable rate for the critical
slowing down in the vicinity of the second-order transition [30]. In connection with
the charge glass state in the valence uctuation compound Sm
3
X
4
X Se or Te
and the spin ladder system Sr
12
Ca
2
Cu
24
O
41
, the ultrasonic dispersion will be again
presented for the latter case in section 4.
3.2. Fe
3
O
4
and Fe
3x
Zn
x
O
4
Probably the oldest investigated charge-ordering phenomenon is the metal
insulator transition occurring at T
V
% 124 K in magnetite Fe
3
O
4
studied by Verwey
[31, 32]. The nature of this transition was suggested to be a charge ordering of Fe
2
Figure 6. The elastic constant c
11
of the longitudinal mode and the attenuation coecient
c
11
for the doped compound Yb
4
(As
1x
Sb
x
)
3
with x 0.29. The anomaly in c
11
and
c
11
around $50 K is the ultrasonic dispersion where the charge uctuation rate
coincides with the frequency of the ultrasonic waves.
and Fe
3
ions, but the details of this mechanism and of the low-temperature
structure do not seem to be settled yet [33].
3.2.1. Introduction
Magnetite undergoes a paramagneticferrimagnetic transition at a much
higher temperature T
C
858 K. This ferrimagnetic order is due to an anti-
ferromagnetic coupling between the A sites (tetrahedral Fe
3
, S
5
2
) and the B
sites (octahedral Fe
3
, Fe
2
, S 2) in the cubic inverse spinel structure with a
space group O
7
h
Fd3m [34]. The magnetic formula can be written as
Fe
3
O
4
Fe
3
tet
Fe
2
Fe
3
oct
O
4
. Upon substitution, the Zn ions occupy only the
tetrahedral sites [35]: Fe
3
1x
Zn
2
x

tet
Fe
2
1x
Fe
3
1x
oct
O
4
.
Magnetite exhibits an anomalous specic heat peak and a large resistance change
at T
V
[36]. The resistance above and below T
V
shows activated temperature
behaviour. This is because the electron hops on the crystallographic B sites. The
charge ordering at T
V
arises because of the Fe
2
Fe
3
ordering on these octahedral
sites. In this structure, the B sites form a network of four tetrahedra within the unit
cell of gure 8, thus constituting a separate unit. The simplest view of charge
ordering on these tetrahedra would be that originally proposed by Verwey [31].
Fe
2
(Fe
3
) cations alone occupy alternating [110] chains as indicated by the broken
lines in gure 8 [3137]. However, this pattern was not veried by the precise neutron
scattering studies [38].
3.2.2. Elastic constants
Elastic constant measurements have been performed for Fe
3
O
4
[39] and
Fe
3x
Zn
x
O
4
[40]. In gure 9, the temperature dependence of the symmetry elastic
constants c
11
, c
11
c
12
2 and c
44
for Fe
3
O
4
with the cubic structure is shown.
Figure 7. The temperature dependence of the relaxation time t due to the charge uctuation
in Sm
3
X
4
X Se or Te, Yb
4
(As
0.71
Sb
0.29
)
3
and Sr
12
Ca
2
Cu
24
O
41
. The thermal
activation-type behaviour t t
0
exp Ek
B
T is reected by the charge glass state or
the partial charge ordering.
Reorientation of the magnetization at 130 K aects the sound propagation very
strongly [39]. In order to avoid such magnetic domain eects, a magnetic eld of
0.5 T was applied for the dierent ultrasonic modes in gure 9. The c
44
mode exhibits
strong softening of about 10% from room temperature down to T
V
124 K. All the
modes exhibit strong rst-order features at T
V
.
Also for the Fe
3x
Zn
x
O
4
system the c
44
mode in gure 10 is the soft mode.
With increasing x the relative softening increases, amounting to 34% for
x 0.032. In addition, the positive step function at T
V
decreases with increasing x
and has disappeared completely for x 0.032, indicating that the structural
Figure 8. Fe ions on octahedral sites of magnetite Fe
3
O
4
, forming four tetrahedra in the
unit cell in the gure with the origin at (0, 0, 0) and with the axis a2: (- - - - -), lines
connecting the tetrahedra along the dierent [110] directions.
Figure 9. Temperature dependences of the elastic constants c
11
, c
11
c
12
2 and c
44
for
Fe
3
O
4
. A magnetic eld of 0.5 T was applied to remove the domains. The softening in
the c
44
mode is due to the coupling to the charge uctuation of the system,
transition is now close to second order. Similar eects can be seen in the other
modes [40].
In contrast with the homogeneously mixed-valence compounds, Poissons ratio
c
12
c
11
c
12
% 0.39 and the bulk modulus c
B
% 2 10
12
erg cm
3
are of rather
a normal order and they show a weak temperature dependence [40]. These quantities
describe the extent of possible valence uctuations [8]. Apparently the charge
uctuations of Fe
2
Fe
3
observed for T T
V
do not alter Poissons ratio and
the bulk modulus c
B
, but they aect very strongly the c
44
mode as shown above.
Poissons ratio may be little aected because only the Fe ions on octahedral sites
exhibit valence hopping and because Fe
3
O
4
is an inhomogeneously mixed-valence
compound in contrast with the homogeneously mixed-valence compounds in 4f-
electron systems [1].
In gure 10 we present the soft mode c
44
for all dierent Fe
3x
Zn
x
O
4
substances
[40]. We plot c
44
Tc
44
270 K as a function of temperature. For T T
V
the
dierent curves for x 0, 0.02 and 0.032 coincide with each other. The values for the
dierent c
44
270 K are given in table 6. Furthermore, the function from equation
(14), c
44
c
0
44
T T
0
C
T Y, gives an excellent t to the curve. This function is
Figure 10. Normalized soft modes c
44
Tc
44
270 K for the Fe
3x
Zn
x
O
4
x 0, 0.02 and
0.032 crystals together with a t () discussed in the text.
Table 6. The Verwey transition temperatures T
V
and elastic constants at 270 K for pure
Fe
3
O
4
x 0 and the substitution compounds Fe
3x
Zn
x
O
4
x 0.02 and 0.032
density j 5.2 g cm
3
.
x
T
V
K
c
11
10
11
erg cm
3
c
12
10
11
erg cm
3
c
44
10
11
erg cm
3
0 124 27.2 17.8 6.1

0.02 94 25.3 14.3 8.4
0.032 83 26.0 14.6 6.5
the expression from Landau theory, indicating a bilinear coupling of the symmetry
strain
xy
to the charge-order parameter Q
xy
for the charge uctuation mode of the
system. For x 0 we obtain for example c
0
44
270 K 6.1 10
11
erg cm
3
,
T
0
c
84.4 K and Y 78.2 K. The energy gain due to the strainorder parameter
coupling g
2
c
0
44
c
0
T
0
c
Y 4.2 K is relatively small.
We plot the Verwey transition temperatures T
V
for the dierent x in gure 11.
Included in this gure are transition temperatures for other substitutions.
Fe
3y
Ti
y
O
4
and o-stoichiometric Fe
31c
O
4
are taken from [41]. Two slopes are
easily recognized in gure 11. These belong to dierent orders of the transition. For
x. y < 0.0125 the phase transition is still rst order, whereas for x. y 0.0125 it is
second order as noted before in gure 10.
3.2.3. Symmetry analysis
Although the charge-order transition at T
V
is very complicated [33, 38], it is
worthwhile making an analogous analysis of pure charge ordering as has been done
for Yb
4
As
3
in the previous section 3.1. The result is the charge order as anticipated
by Verwey [31]. The space group of the cubic magnetic structure above T
V
is O
7
h
Fd3m and a cubic unit cell contains eight chemical formula units. The octahedral B
sites form four tetrahedra as shown in gure 8. In order to determine the coupling of
the charge uctuation mode to the elastic strain, we consider just one such
tetrahedron with T
d
symmetry. The other tetrahedra are obtained by translation
vectors. The character table for this symmetry is given in table 7. We denote the
charge densities for the Fe
2
and Fe
3
ions in such a tetrahedron by j
i
i 1. 2. 3. 4.
The charge densities at tetrahedron sites have coordinates such as j
1
j
1
"
11.
"
11.
"
11,
j
2
j
2
"
11. 1. 1, j
3
j
3
1.
"
11. 1 and j
4
j
4
1. 1.
"
11. One can also see these sites in
gure 12. The average valence of these charges is 2.5e. In the following, we use the
method of calculations presented in the theory in section 2 and applied to the case of
Yb
4
As
3
in section 3.1.
Application of the 24 symmetry operations of T
d
to j
i
gives a reducible
4 4 matrix representation. This can be decomposed into a sum of irreducible
Figure 11. Plot of the Verwey transition temperature T
V
versus concentration x (Zn, Ti or
O). Adapted from Kozlowski et al. [41] and gure 10.
representations. The character .
tet
s of the reducible representation is also given in
table 7. It decomposes into the two irreducible representations A
1
T
2
. Since the
direct product T
2
T
2
contains A
1
, there are charge uctuation modes of these
symmetries. The order parameter Q
yz
, Q
zx
, Q
xy
with T
2
symmetry couples bilinearly
to the elastic strains
yz
,
zx
,
xy
of the c
44
mode with the same symmetry and
furthermore there is a coupling to the volume strain
B
of the bulk modulus c
B
with
A
1
symmetry. The coupling of Q
A1
to the volume strain
B
, however, has no eect on
the charge ordering in Fe
3
O
4
.
In the Fe
3x
Zn
x
O
4
system, the important strain coupling is to the c
44
mode
as discussed before in gures 9 and 10. As shown above, we can have a bilinear
coupling of the strain
T
2
and the charge uctuation mode Q
T
2
as, F
b1

g
5
Q
yz
yz
Q
zx
zx
Q
xy
xy
, which was already presented in equation
(10) in section 2.2. This coupling leads to the elastic constant expression,
c
44
c
0
44
T T
0
c
T Y of equations (14) and (21). As was discussed in section
3.2.2, the experimental results on c
44
of our system in gure 10 are nicely explained
by equation (21).
We have not yet discussed the nature of the order parameter in the Landau
analysis. This we shall do again for the case of a single tetrahedron considered above.
Using the projection operator techniques as outlined in section 2.1, we obtain for the
charge uctuation modes the following expressions in table 8.
For the Landau theory, the change j in the charge density across the charge-
ordering point is described by j
T
2
.yz
, j
T
2
.zx
and j
T
2
.xy
on T
2
symmetry:
j Q
yz
j
T
2
.yz
Q
zx
j
T
2
.zx
Q
xy
j
T
2
.xy
. 18
0

Figure 12. Charge uctuation modes of (a) j
T
2
.xy
and (b) j
A
1
the Fe
3
O
4
tetrahedra. The
elastic softening of c
44
leads to the charge order of j
T
2
.xy
in (a), which was anticipated
by Verwey [31].
Table 7. The character .
tet
s of the reducible representation for the charge uctuation modes
for T
d
point-group symmetry in Fe
3
O
4
.
Character E 6IC
4
3C
2
6o
d
8C
3
.
A
1
s 1 1 1 1 1
.
A
2
s 1 71 1 71 1
.
T
1
s 3 1 71 71 0
.
T
2
s 3 71 71 1 0
.
tet
s 4 0 0 2 1
Here the coecients Q
yz
, Q
zx
and Q
xy
are the order parameters to describe charge
ordering of the B sites. They are zero j 0 in the high-temperature phase above
T
V
. From this analysis we can determine the possible charge distribution in the
ordered phase T < T
V
. j
A
1
would correspond to an average valence of 2.5e at
each ion site in the tetrahedron. For j
T
2
.yz
. j
T
2
.zx
and j
T
2
.xy
there are dierent
possibilities depending on whether just one component of the order parameter,
say, case (i) Q
xy
6 0 and Q
yz
Q
yz
0 or case (ii) when two components are not
equal to zero or case (iii) when all three components are not equal to zero. Since the
low-temperature structure in magnetite still remains to be solved [33], we shall not
discuss all these possibilities except to note that for an orthorhombic subgroup C
2v
of T
d
we have the rst-mentioned case Q
xy
6 0. The orthorhombic structure C
2v
would be the low-temperature structure if one neglects the monoclinic tilt angle u
[34]. This order parameter would lead to a charge distribution of Fe
2
along the [110]
direction and Fe
3
along the other [011] of gure 8. This gives a charge ordering
anticipated before by Verwey [31]. These charge distributions for j
A
1
and j
T
2
.xy
are
shown in gure 12.
Recent X-ray scattering experiments of Fe
3
O
4
give a confusing picture of the
charge ordering below the Verwey transition. One resonant X-ray experiment gives
no indication of charge uctuation above T
V
and charge ordering below T
V
[42].
This is in contrast with two other similar X-ray experiments, which show charge-
ordering phenomena [43, 44]. The latter paper, giving high-resolution X-ray and
neutron powder diraction data, proposes a charge order on the B sites below T
V
,
which is not the Verwey charge order discussed above. Therefore other factors than
our charge order model inuence the strong rst-order transition and the resulting
charge order. A model based on simultaneous ordering of charge and orbital states
deduced from nuclear magnetic resonance (NMR) spectrum of Fe
3
O
4
[45] is a way to
characterize the rst-order transition at T
V
. The transition from the Verwey state of
the insulator into a metallic state around 8 GPa at T 0 K is an important
indication for delocalization of 3d electrons in magnetite [46]. Apparently the issue
of the Verwey transition in Fe
3
O
4
is not settled yet.
3.3. NaV
2
O
5
A very interesting compound exhibiting charge uctuation and a charge-ordering
transition is c
0
-NaV
2
O
5
. It belongs to the family of vanadium oxides with the
chemical formula MV
2
O
5
with M the metallic ion (Li or Na with monovalence, and
Mg or Ca with divalence). Depending on the valence of these ions we can have V
4
or V
5
. The magnetic ion V
4
(3d
1
) has spin S
1
2
whereas V
5
(3d
2
) has an empty 3d
Table 8. Charge uctuation modes for a tetrahedron with T
d
point group symmetry in Fe
3
O
4
.
Symmetry Charge uctuation mode Elastic strain
1
A
1
j
A
1
j
1
j
2
j
3
j
4

B

xx
yy
zz
3
E
u
2
zz
xx
yy
3
p
v

xx
yy
5
T
2
j
T
2
.yz
j
1
j
2
j
3
j
4
j
T
2
.zx
j
1
j
2
j
3
j
4
j
T
2
.xy
j
1
j
2
j
3
j
4
yz
zx
xy
shell. All substances of this series are isostructural and consist of planes of V
2
O
3
double chains. These planes are separated through non-magnetic M planes. The
thermodynamic properties of NaV
2
O
5
have been thoroughly discussed recently [47].
3.3.1. Introduction
NaV
2
O
5
was initially believed to consist of two leg ladders with space group C
7
2v
P2
1
mn in which charge segregation occurs in a way that one leg of each ladder has
V
4
and the other V
5
ions [48]. However, recently four dierent crystallographic
investigations showed that the structure is centrosymmetric (space group, D
13
2h
Pmmn) with all V atoms crystallographically equivalent at room temperature [49
52]. This result agrees with
51
V NMR experiments, which showed the presence of
only one type of V atom at room temperature [53, 54]. Raman-active phonon modes
are consistent with the Pmmn space group [55, 56]. Therefore this compound is a
mixed-valence system with an average valence of V
4.5
(3d
1.5
). It can be considered as
a quarter-lled ladder compound in a one-electron band picture [50, 57] and it is
therefore a MottHubbard insulator. In gure 13 we show the ion arrangement for
NaV
2
O
5
.
A phase transition occurs in NaV
2
O
5
at T
C
% 34 K. Below T
C
the susceptibility
changes rapidly [58] and a lattice distortion with a resulting supercell of 2a 2b 4c
results [59]. This does not lead to a spin-Peierls transition as originally thought but
rather to a charge-ordering transition. In particular the
51
V NMR results, which
gave just one line for T T
C
show the presence of two lines of inequivalent V
4
and
V
5
below T
C
[54, 60]. Electron spin resonance experiments give, owing to
dimerization, a singlettriplet gap of 90 20 K for the V
4
ion for T < T
C
[6164].
Thermal expansion and specic heat measurements gave evidence for two
consecutive transitions; a sharp rst order-like transition at about 33 K and a
second-order-like transition at about 34 K [65]. More recently a synchrotron
radiation X-ray diraction experiment [66] gave evidence for a orthorhombic
monoclinic phase transition.
3.3.2. Elastic constants
Here we give a survey of elastic constant measurements for the two systems
CuGeO
3
and NaV
2
O
5
. It is instructive to compare the elastic modes for these two
compounds in order to see clearly the similarities and dierences between a
compound exhibiting a spin-Peierls transition and a compound exhibiting a
Figure 13. c
0
-NaV
2
O
5
view along the b direction. Black circles indicate the Na ions; the V
ions are inside the pyramids; the O ions are at the corners of the pyramids.
charge-order transition. We start with a presentation of results for the longitudinal
c
22
and c
33
modes for the two compounds, where we compare the results of Schwenk
[67] with those from other groups [68, 69]. Afterwards we present the important
shear modes.
For the longitudinal modes, we compare rst the c
22
mode in NaV
2
O
5
with the
c
33
mode in CuGeO
3
because the chain direction is the b axis in the former and the c
axis in the latter. In gure 14 (taken from [67, 70]) we compare these modes as a
function of TT
C
. The softening of the c
22
mode (NaV
2
O
5
) starts at a much higher
temperature than the c
33
mode (CuGeO
3
) does. In the simple Landau picture
without uctuation eects discussed in section 2, one expects a step function at
the transition temperature T
C
. This is approximately the case for CuCeO
3
but not
for NaV
2
O
5
. In the latter case, strong thermal uctuations had to be considered, as
already observed from specic heat experiments [71]. A theory for elastic constants
in the presence of thermal uctuations has been given by Henkel et al. [72].
The longitudinal modes of the two compounds also dier in another important
aspect: whereas for CuGeO
3
only the c
33
mode along the chain shows an anomaly at
T
C
[68], in NaV
2
O
5
both modes c
22
(along the b axis, direction of the ladder) and c
33
(along the c axis) exhibit anomalies [70]. This is typical for a (purely one-
dimensional) spin-Peierls transition versus a charge order transition.
Next we discuss the shear modes for the two crystals. Here we compare the shear
c
66
and c
55
modes of NaV
2
O
5
and the shear c
55
and c
44
modes of CuGeO
3
. For the
latter substance, both modes have the propagation direction along the chain
whereas, for NaV
2
O
5
, the c
66
mode has the propagation direction along the b axis
and polarization along the a axis, both in the plane of the ladder and c
55
has the
polarization along the c direction. Figure 15 shows the temperature dependence of
these shear modes in both compounds NaV
2
O
5
and CuGe
2
O
3
. The two shear modes
for CuGeO
3
have normal temperature dependences with a very small anomaly at T
SP
amounting to less than 10
4
in the relative velocity change not visible in gure 15.
For NaV
2
O
5
the c
55
mode has an anomaly for T < 55 K, arising partly from the
interference with the accompanying c
66
mode, which itself shows strong softening.
Figure 14. Comparison of longitudinal modes along the chain directions for CuGeO
3
(c
33
)
and NaV
2
O
5
(c
22
). (After Schwenk et al. [40].)
The overall eect for c
55
is of the order of 1 part in 10
3
. The most important mode c
66
behaves as a soft mode, the softening starting from 80 K and the total amount of
change down to T
C
is 7% in the relative velocity. Below T
C
% 34 K the ultrasonic
echo disappears completely until 13 K with the propagation direction along the a
axis and polarization along the b axis.
We can interpret the strong softening of the c
66
mode for T T
C
with the aid of
a bilinear coupling between the strain
xy
and the corresponding order parameter
Q
xy
of the same symmetry, as discussed in section 2.2. In gure 16 we show the result
of a t using equation (14) in section 2.2. The background elastic constant is taken
with an empirical expression [73] as the broken curve. We nd an almost perfect t
with the Landau formula c
66
c
0
66
T T
0
c
T Y obtaining (with an extra-
Figure 15. Temperature dependences of the relative sound velocities (a) of shear c
55
and c
66
modes for NaV
2
O
5
and (b) of c
55
and c
44
for CuGeO
3
. (After Schwenk et al. [70].)
Figure 16. Temperature dependence of the c
66
mode in NaV
2
O
5
together with a t as
discussed in the text: (- - - - -), background.
polated c
66
!0) T
0
c
30.62 K and Y 30.34 K. Consequently, the strainorder
parameter coupling is rather small, g
2
c
0
c
0
66
T
0
c
Y 0.28 K, much smaller than
in the case of Fe
3
O
4
or Yb
4
As
3
. Therefore, the softening starts at relatively low
temperatures around 80 K. The physical nature of the order parameter has not been
specied yet.
3.3.3. Symmetry analysis for charge ordering in NaV
2
O
5
From various experiments (see sections 3.3.1 and 3.3.4) we know that the unit cell
is enlarged to 2a. 2b. 4c in the ordered region. This means that the charge uctuation
mode responsible for the charge order has a propagation vector k
1
2
.
1
2
.
1
4
. There-
fore, we cannot perform the same analysis as for Yb
4
As
3
, coupling the c
66
strain
component to the charge order parameter. However, it is instructive to perform a
symmetry analysis on the unit cell given in gure 17. We consider as the basis for
simplicity the four atoms as shown in gure 17. With this basis and the three
displacement vectors we can build up the V lattice as shown in gure 17. The four
basis ions have the symmetry D
2h
. Owing to the even character of the strains we have
to consider only the character table for the point group D
2
in table 9. The elastic
constant c
66
propagates along the b axis with polarization along the a axis or vice
versa. The corresponding strain is
xy
and has therefore B
1
symmetry (see table 9).
The ions of our basis are labelled j
1
. j
2
. j
3
and j
4
as shown in gure 17. The
symmetry elements of D
2
acting on the basis ions give a reducible representation of
D
2
called
cf
. With the help of the character table,
cf
in table 9 can be split into a
direct sum of irreducible representations
cf
A
1
B
1
B
2
B
3
. All irreducible
representations are containined in
cf
, especially A
1
and B
1
. In the high-temperature
Figure 17. Projection of the V atoms in the ab plane of NaV
2
O
5
. Atoms 14 are used for
the symmetry analysis in the text.
Table 9. Character table for the charge uctuation mode in NaV
2
O
5
with D
2
symmetry.
Character E C
z
2
C
y
2
C
x
2
Bases
.
A
1
s 1 1 1 1 x
2
. y
2
. z
2
.
B
1
s 1 1 71 71 xy
.
B
2
s 1 71 1 71 zx
.
B
3
s 1 71 71 1 yz
.
cf
s 4 0 0 0
phase, charge uctuations with A
1
symmetry are present and are equally distributed
on all four basis atoms. At T
C
the elastic mode B
1
becomes soft and the charges
order accordingly.
For one-dimensional representations the projection operator can be written as
P
j

1
4
P
i
.
j
i
P
j
i
by equation (7) in section 2.1 [17]. One obtains the charge
uctuation mode for NaV
2
O
5
as shown in table 10. In gure 18 the dierent charge
distributions are shown. For all atoms the total symmetric charge uctuation mode
of j
A
1
j
1
j
2
j
3
j
4
has the same weight. Therefore, in the high-temperature
phase all atoms carry the same charge 4.5e. For the B
1g
mode the basis is
j
B
1
j
1
j
2
j
3
j
4
. Therefore, in condensing the j
B
1
mode with j Q
B
1
j
B
1
,
we obtain zigzag order. With this ordering the unit cell doubles in the a and b
directions in agreement with X-ray diraction results [59]. Before discussing the B
1
symmetry for the charge-ordered state any further, it should be noted that the
longitudinal sound wave modes in NaV
2
O
5
have A
1
symmetry (as seen from table 9).
Because B
1
B
1
A
1
the longitudinal modes couple quadratically to the order
parameter.
3.3.4. Other indications favouring a zigzag structure
Various theoretical and experimental approaches favour such a zigzag structure
as discussed above. In our analysis given above, we have considered only one ladder
Figure 18. Charge uctuation modes j
A
1
. j
B
1
. j
B
2
and j
B
3
for the dierent charge
distributions in NaV
2
O
5
: (*), integer valence V
4
; (*) V
5
, integer valence; (8),
fractional valence V
4.5
. j
B
1
is the symmetry deduced from our analysis.
Table 10. Charge uctuation mode of NaV
2
O
5
with D
2
symmetry.
Symmetry Charge uctuation mode Strain
1
A
1
j
A
1
j
1
j
2
j
3
j
4

xx
.
yy
.
zz
2
B
1
j
B
1
j
1
j
2
j
3
j
4

xy
3
B
2
j
B
2
j
1
j
2
j
3
j
4

zx
5
B
3
j
B
3
j
1
j
2
j
3
j
4

yz
in the b direction. As we cannot say anything about the coupling between adjacent
ladders, the zigzag arrangement in this analysis is conned to one ladder.
The actual zigzag arrangement occurring in NaV
2
O
5
is still not denitely known.
Various synchrotron X-ray diraction investigations and neutron diraction experi-
ments give conicting results. All experiments give a zigzag charge order but some
give fully charged ladders as shown in gures 19 (a) and (b) [66, 74]. This is in
agreement with NMR results [54, 60] where only lines from V
4
and V
5
are found.
However, another class of similar experiments give charge ordering in alternate
ladders as shown in gure 19 (c) [7577]. This latter structure has three inequivalent
V sites V
4
. V
4.5
and V
5
with the space group C
18
2v
Fmm2.
Theoretically considering the on-site and intersite Coulomb interaction within
the ladder as well as between ladders, superexchange models based on the Hubbard
Hamiltonian at half-lling were employed. The dierent Coulomb repulsions create
a charge-transfer gap, making NaV
2
O
5
an insulator. In the theoretical models, fully
charged ladders were found as well as alternate charge ordering. Relevant theoretical
papers are [50, 7882]. In gure 19 we give the dierent possible charge ordering
patterns discussed above, taken from [81].
Another indication for the zigzag structure is the occurrence of two magnon
branches observed by neutron scattering along the a axis [83, 84]. The point made is
the existence of dierent exchanges between the ladders, which lead to dispersion
and splitting of the magnon bands [85]. The dierent exchange parameters are
possible for a zigzag charge arrangement.
Let us return to the fully charged zigzag ladder. In addition to this charge
ordering, a phase transition from orthorhombic to monoclinic structure was found
at T
C
[66]. The monoclinic structure has a 6 b 6 c and 6 p2. This means that the
spontaneous strain is
xy
6 0. The accompanying soft mode is c
66
, the mode which
was found to soften by 14% before the disappearance of the ultrasonic echoes. The
c
66
mode softening cannot be due to bilinear coupling to the charge order parameter
as outlined above, but rather due to a coupling to a structural order parameter of B
1
(b) (c)
Figure 19. Charge-ordering models for NaV
2
O
5
: (*), V
4
; (*), V
5
; (8), V
4.5
. For a
discussion see text [81].
(a)
symmetry (see table 9). Evidence for a structural transition near T
C
has been found
before from thermal expansion experiments as discussed above [65] and also from
anomalies in the longitudinal sound velocity [70]. All these recent experiments show
that the low-temperature charge ordering of NaV
2
O
5
is still not yet completely
solved.
4. Applications: Systems exhibiting a charge glass state or partial charge ordering
4.1. Sm
3
X
4
4.1.1. Glass state in Sm
3
X
4
The samarium chalcogenides Sm
3
X
4
(XS, Se or Te) with the cubic Th
3
P
4
structure of the space group symmetry T
6
d
exhibit an inhomogeneous valence
uctuation system with coexisting divalent Sm
2
and trivalent Sm
3
ions. It is noted
that the role of cations and anions in Sm
3
X
4
are reversed compared with Yb
4
As
3
discussed before in section 3.1. In Sm
3
X
4
the divalent Sm
2
ion of 4f
6
possesses the
ground-state multiplet
7
F
0
and the excited state
7
F
1
at 400 K, and the trivalent Sm
3
ion of 4f
5
has the ground-state multiplet
6
H
52
. The magnetic susceptibility of Sm
3
X
4
is well explained by a sum of the Van Vleck terms of J 0 (0 K) and J 1 (400 K) in
Sm
2
and the Curie term of J
5
2
in Sm
3
in the ratio NSm
2
: NSm
3
1 : 2.
The activation-type temperature dependence of the dc resistivity j j
0
expEk
B
T
has a unique value of the activation energy E % 0.14 eV for Sm
3
X
4
(XS, Se or Te).
Furthermore, careful measurements of the high-frequency dielectric response of
Sm
3
Se
4
by means of an impedance analyser up to 1 GHz at low temperatures reveal a
high-frequency dielectric dispersion of the ColeCole type [86]. The relaxation time
exhibits an activationtype temperature dependence as t t
0
exp Ek
B
T with a
characteristic time t
0
2.4 10
13
s and the same activation energy E % 0.14 eV
quoted above from dc resistivity. The analysis for the dielectric response conrmed
that Sm
3
Se
4
is an insulator, that is without free carriers at low temperatures.
The elastic constant measured by ultrasound with frequencies 10 MHz of
Sm
3
Se
4
in gure 20 shows a step-like increase around 120 K [14]. This anomaly is
caused by the ultrasonic dispersion where the thermal uctuation time t coincides
with the characteristic frequency . of the ultrasonic wave. The elastic constant c.
and the attenuation coecient c. of the transverse c
44
mode in Sm
3
Se
4
in gure 21
are well described by the ultrasonic dispersion with the relaxation time t [87]:
c. c1
c1 c0
1 .
2
t
2
. 22 a
c.
c1 c0
2ji
3
1
.
2
t
1 .
2
t
2
. 22 b
The relaxation time t corresponds to the hopping rate in the thermal motion of the
4f electron from Sm
3
to neighbouring Sm
2
ions in Sm
3
X
4
. The dispersion of
Sm
3
X
4
(XS, Se, or Te) is governed by the activation-type temperature dependence
t t
0
exp Ek
B
T with common parameters of the activation energy E % 0.14 eV
and t
0
2.4 10
13
s, as shown already in gure 7. The relaxation time
t % 5 10
11
s at 300 K changes to t % 10
57
s at the low temperature of 10 K. Even
though the relaxation time t becomes longer and longer on lowering the temperature
in Sm
3
X
4
(XS, Se or Te), no sign of a phase transition to a charge-ordered state
has been found. This result is in contrast with the critical slowing down of the order
Figure 20. Temperature dependence of the elastic constants of Sm
3
Se
4
. Anomalous steps
around 120 K are caused by the ultrasonic dispersion where the frequency 10 MHz of
the sound waves coincides with the valence uctuation rate of the system.
Figure 21. Ultrasonic dispersion of the elastic constant c
44
. and the attenuation
coecient c
44
. in Sm
3
Se
4
. c0 and c1 are the low- and high-frequency limits
respectively.
parameter uctuation rate in the vicinity of the second-order phase transition point
[30]. In lowering the temperature the uctuation of the 4f electrons in the present
system of Sm
3
X
4
freezes gradually into a charge glass state, which is characterized by
the random distribution of Sm
2
and Sm
3
ions in space. In fact, it has been
reported that the broad peaks of the magnetic susceptibility and specic heat around
T
sg
1.3 K in Sm
3
Te
4
corresponds to the transition into the spin-glass state because
of the random ordering of the magnetic moments of Sm
2
and Sm
3
ions [88].
4.1.2. Two-level system in Sm
3
Te
4
It has recently been found that the elastic constants of Sm
3
Te
4
show a
characteristic decrease proportional to ln T in the low-temperature region below
15 K down to the spin-glass transition temperature T
sg
1.3 K [89]. The result of the
transverse c
11
c
12
2 mode of Sm
3
Te
4
is shown in gure 22. The other transverse
c
44
mode and the longitudinal c
11
mode also exhibit a similar decrease proportional
to ln T. It is already known that the glassy compounds show some characteristic
properties: a specic heat proportional to T, a thermal conductivity proportional to
T
2
and a decrease in the elastic constant with ln T at low temperatures. These
properties are described in terms of the two-level system due to the tunnelling ionic
motion in random potential of glass compounds [90, 91]. Even though the present
crystal of Sm
3
Te
4
is of high quality, the Sm
2
and Sm
3
ions freeze with random
spatial distribution at low temperatures. Therefore, the 4f electrons in the random
potential of Sm
3
Te
4
may tunnel from the divalent Sm
2
ion of 4f
6
to the trivalent
Sm
3
ion of 4f
5
located at the nearest-neighbour sites. The tunnel motion of the 4f
Figure 22. Low-temperature softening proportional to ln T in the elastic constant
c
11
c
12
2 of Sm
3
Te
4
. This softening is due to the two-level states responsible
for the 4f tunnelling motions in the charge glass. The minimum around 1.2 K
indicates the spin-glass transition.
electrons is relevant when the initial and nal states possess nearly equal energies. In
analogy to the two-level system of the ionic tunnel motion in glasses, the decrease in
the elastic constant can be written as
c
c

cT cT
0
cT
0
2 v
v
2p
2
jv
2
ln
T
T
0

2K ln
T
T
0

. 23
Here c is the elastic constant and v is the velocity of ultrasound with v the sound
velocity change. p is the density of state for the two-level systems and is a coupling
constant of the elastic strain to the tunnelling state. T
0
is a characteristic temperature
of the system. The solid line in gure 22 is obtained with the parameters
p
2
52 10
8
erg cm
2
, jv
2
3.73 10
11
erg cm
3
and K 2p
2
ji
2
1.4 10
4
.
These parameters of Sm
3
Te
4
agree well with the results on borosilicate glass, vitreous
silica and metallic glass of Pd
78
Si
16
Cu
6
[90].
The numerical value of the coupling constant of Sm
3
Te
4
is not clear at the
present stage. It is expected that the tunnelling of the 4f electrons is available for the
pair of the nearest-neighbour Sm
2
and Sm
3
conguration with equal energy states.
The evaluation of the probability to nd the pair of Sm
2
and Sm
3
ions exhibiting
4f tunnel motion remains to be solved.
4.1.3. Possible charge ordering in Eu
3
S
4
Because Eu
3
S
4
has the same structure as Sm
3
X
4
and charge ordering at
T
C
180 K [15], it is very interesting to compare the two compounds in detail.
Why does Sm
3
X
4
favour the charge glass state and does not exhibit charge
ordering with the usual second-order transition with symmetry-breaking character
like Yb
4
As
3
? Looking for the origin of the charge glass state in Sm
3
X
4
, it is
worthwhile to show the symmetry character of the charge uctuation modes in the
system with the Th
3
P
4
structure. We present a candidate for the charge uctuation
mode, which freezes at the charge-ordering point in the isomorphous compound
Eu
3
S
4
.
Similar to the case of Yb
4
As
3
with the anti-Th
3
P
4
structure, the four molecular
units are involved in the conventional unit cell of Sm
3
X
4
and Eu
3
S
4
with the
Th
3
P
4
structure. The charge densities j
i
i 1. 2. . . . . 6 for the 4f electrons at the
crystallographically equivalent ith Sm or Eu sites are introduced. The 24 symmetry
operators s fRjbg of the space group T
6
d
I
"
443d in table 2 act on the charge densities
j
i
i 1. 2. . . . . 6. Then we obtain the representation matrix Ds with 6 6
dimensions. The character for the charge uctuation modes in Sm
3
X
4
is given by
the trace of the representation matrix in equation (4) as shown in table 11. This
character .
cf
s of table 11 is reduced to A
1
1d E2d T
1
3d. The projection
operator of equation (6) provides the bases of the irreducible representation for the
charge uctuation modes in Sm
3
X
4
and Eu
3
S
4
.
The charge neutrality with the coexistence ratio NSm
2
: NSm
3
1 : 2 in
Sm
3
X
4
constrains the charge distribution in table 12. The charge uctuation mode
j
A
1
j
1
j
2
j
3
j
4
j
5
j
6
with full symmetry represents the uniform charge
distribution over all the R sites with a mean valence
8
3
e. On the other hand, the
charge uctuation modes with the symmetry-breaking character of E and T
1
lead to
the anisotropic charge distribution over the six Sm-ion sites. The charge uctuation
mode of j
E.u
j
1
j
2
j
3
j
4
2j
5
2j
6
in gure 23 with the u component of
the E doublet presents the charge distribution of the trivalent 3e at Sm(1), Sm(2),
Sm(3) and Sm(4) sites and the divalent 2e at Sm(5) and Sm(6) sites. The mode
j
E.v
j
1
j
2
j
3
j
4
, however, means the distribution of the fractional charges
7
3
e at Sm(1) and Sm(2) sites,
8
3
e at Sm(5) and Sm(6) sites, and integer charge 3e at
Sm(3) and Sm(4) sites. In the case of the charge uctuation mode j
T
1
.x
j
1
j
2
of
the x component of the T
1
triplet, the integer charge of 3e is located at Sm(1), the
fractal charges
7
3
e is at Sm(2), and
8
3
e is at Sm(3), Sm(4), Sm(5) and Sm(6) sites.
Other j
T
1
.y
j
3
j
4
and j
T
1
.z
j
5
j
6
also consist of the integer charge 3e,
and the fractional charges
7
3
e and
8
3
e at appropriate Sm sites [89].
The correlated motion of the 4f electrons dominated by thermally activated
processes leads to the fractional charge distribution at Sm sites. At low temperatures
far below the activation energy E % 0.14 eV (1600 K), however, the thermal
activation motion of the charge uctuation dies out completely. Therefore, only
the charge uctuation mode with the integer valence in units of e realizes charge
ordering at low temperatures. In this context the charge uctuation mode j
E.u
, which
consists of integer charge distribution of 2e and 3e, is a candidate for the charge
ordered phase in the valence uctuation compounds with the Th
3
P
4
-type structure.
Table 11. Character table for the charge uctuation mode in Sm
3
X
4
and Eu
3
S
4
with the space
group symmetry T
6
d
.
Character E 8IC
4
3C
2
6o
d
8C
3
.
A
1
s 1 1 1 1 1
.
E
s 2 0 2 0 71
.
T
1
s 3 1 71 71 0
.
cf
s 6 1 1 0 0
Table 12. The bases of the irreducible representation for the charge uctuation modes and the
elastic strains in Sm
3
X
4
and Eu
3
S
4
with the Th
3
P
4
structure.
1
A
1
j
A
1
j
1
j
2
j
3
j
4
j
5
j
6

B

xx
yy
zz
3
E j
E.u
j
1
j
2
j
3
j
4
2j
5
2j
6
j
E.v
j
1
j
2
j
3
j
4
u
2
zz
xx
yy
3
p
v

xx
yy
4
T
1
j
T
1
.x
j
1
j
2
j
T
1
.y
j
3
j
4
j
T
1
.z
j
5
j
6
5
T
2

yz
zx
xy
The order parameter Q
E.u
for j
E.u
may couple with the tetragonal strain
u
2
zz
xx
yy
3
p
with the same symmetry. The orthorhombic strain
v

xx
yy
couples to Q
E.v
of the charge uctuation mode j
E.v
. The strainorder
parameter coupling is written as (see equation (10))
F
bl
g
3
Q
E.u
u
Q
E.v
v
. 24
It is expected, therefore, that the freezing of j
E.u
at the charge-ordering point, namely
Q
E.u
6 0 below T
C
, gives rise to the structural change from cubic to tetragonal
lattices
u
6 0.
It is known that the isomorphous compound Eu
3
S
4
consisting of Eu
2
and Eu
3
ions in the ratio NEu
2
: NEu
3
1 : 2 exhibits charge ordering at T
C
186 K.
The thermal expansion measurement on the charge ordering of Eu
3
S
4
shows a
structural change at T
C
[15]. Quite recently an X-ray measurement revealed that the
crystal structure of Eu
3
S
4
changes from cubic to tetragonal [43], which is consistent
with the present analysis based on the equation (24) [89].
The Madelung energy due to the electrostatic energy based on the point-charge
model shows that the charge uctuation mode of j
E.u
in gure 23 possesses the
lowest energy. Furthermore, the uniform distribution of j
A
1
has a high Madelung
energy corresponding to the excited state. This estimate of the Madelung energy
supports the above mentioned scenario for the charge order of j
E.u
in Eu
3
S
4
[21]. The
compounds Sm
3
X
4
(XS, Se or Te), however, do not exhibit charge ordering and
favour the charge glass state at low temperatures. This means that the charge
uctuation mode of j
E.u
with the integer charge of unit e belongs to the excited state
in Sm
3
X
4
and the mode with fractional charge, for instance j
T
1
, is the ground state
of the system. When the thermal activation motion dies out at low temperatures, the
localization of the 4f electrons gives rise to the charge glass state with the random
distribution of the integer valences 2e or 3e in Sm
3
X
4
. In fact, the Monte Carlo
method by Iyetomi et al. [21] has shown that there exists many charge congurations
continuously approaching the ground state. This result promises a charge glass state
nally reached by cooling processes. The dierence between the charge glass state in
Sm
3
X
4
and the charge ordering in Eu
3
S
4
could be the dierent hybridization eect of
the 4f electrons with 3p electrons of chalcogenides.
Figure 23. A possible charge ordering of Eu
3
S
4
with the cubic Th
3
P
4
crystal structure
anticipated in the analysis by Nemoto et al. [89].
4.2. Sr
14
Cu
24
O
41
and Sr
12
Ca
2
Cu
24
O
41
Sr
14
Cu
24
O
41
is a substance containing spin ladders and spin chains. It contains
similar spin-ladder planes as in SrCu
2
O
3
. See gure 24 for an illustrated view of this
substance. In the upper part of gure 24, we show the schematic arrangement of the
chains and ladders. There are predictions that spin ladders with even number of
chains (odd number of rungs) become superconductors with hole doping [92]. Unlike
the ordinary spin chains, Sr
14
Cu
24
O
41
can be doped easily and Sr
2.5
Ca
11.5
Cu
24
O
41
becomes superconducting under a high pressure of 6 GPa [93]. This is one of the
reasons why these substances are interesting [94].
Figure 24. Structure of Sr
14
Cu
24
O
41
: upper diagrams, chains and ladders; lower diagram,
view of the structure in the c direction.
The compound Sr
14x
Ca
x
Cu
24
O
41
possesses layered structures of alternating
Cu
2
O
3
and CuO
2
sheets, which are separated by Sr and Ca layers. The Cu
2
O
3
layers
consist of two leg spin ladders. The approximately 1808 CuOCu bonds give rise to
a strong antiferromagnetic-type superexchange coupling between the Cu spins along
the legs and rungs. The CuO
2
planes are composed of spin chains of edge-sharing
CuO plaquettes (see gure 24).
Independent of the Ca concentration, the average Cu valence in
Sr
14x
Ca
x
Cu
24
O
41
is 2.25e; that is, the compound is intrinsically doped with six
holes per formula unit. In the chains the average valence is 2.6e. They form a
reservoir of charges for the spin ladders. The chains have a small spin gap of about
120 K [95, 96] and the spin ladders of 400500 K [97, 98]. The spin dimers in the
chain are found between next-nearest-neighbour Cu spins [99] that are separated by
localized ZhangRice singlets, i.e. by a site occupied by a localized hole. Neutron
diraction [100, 101] as well as X-ray scattering experiments [102] in Sr
14
Cu
24
O
41
reveal a periodic spacing of spin dimers together with an additional structural
periodicity, which indicates charge ordering in the chains. This is corroborated by
electrical resistivity data [103], by an anomaly in thermal expansion [104] and by our
elastic constant data [67, 96] shown below.
To study this charge ordering with elastic waves, we rst discuss Sr
14
Cu
24
O
41
. In
contrast with Yb
4
As
3
or Fe
3
O
4
, there is no bilinear coupling of the strain to the
order parameter at jkj % 2p5c. Therefore, there is no elastic soft mode but for the
longitudinal modes c
11
and c
33
anomalies at 100 and 220 K can be seen in gure 25.
These anomalies are suprisingly stronger for the c
11
mode with the propagation
direction perpendicular to the chain than for c
33
propagating along the chain. The
same eect occurs also in thermal expansion, which exhibits stronger eects along
the a axis than along the c axis [104]. Obviously the a-axis coupling constant is larger
than the c-axis coupling. No charge-order phase transition occurs, however.
Furthermore, the eect of length changes on the second velocity due to thermal
expansion is negligible.
In Sr
12
Ca
2
Cu
24
O
41
(gure 26 (a)) the anomalies seen for the c
33
mode occur
again in the same region as the thermal expansion anomalies. In addition, the
sound velocity and the attenuation show strong frequency-dependent eects. The
Figure 25. Temperature dependence of longitudinal modes c
11
and c
33
for Sr
14
Cu
24
O
41
.
attenuation maximum increases with increasing frequency. This can be described as
a relaxation process as used before in equations (22 a) and (22 b). The relaxation time
shows the thermal activation type of behaviour t t
0
exp Ek
B
T. This is the time
for the holes in the chain to change their positions. E is the activation energy for such
a site change. With a model calculation as shown in gure 26 (b), we obtain
t
0
1.01 10
13
s and E 1900 K. These dispersion measurements are also in-
cluded in gure 7 together with Sm
3
X
4
(XSe or Te) and Yb
4
(As
1x
Sb
x
)
3
.
5. Applications: charge and orbital orderings in colossal-magnetoresistance
materials
5.1. La
1x
Sr
x
MnO
3
5.1.1. Colossal magnetoresistance and orbital ordering
It has recently been found that the manganese oxides La
1x
Sr
x
MnO
3
,
Nd
1x
Sr
x
MnO
3
and Pr
1x
Ca
x
MnO
3
with the cubic perovskite structure in gure
27 exhibit a eld-induced metalinsulator transition [105107]. This remarkable
eect is the CMR. It has been known since the 1950s that the double-exchange
interaction resulting from electron transfer between adjacent Mn
3
and Mn
4
ions
via the O 2p orbital brings about the ferromagnetic metallic state in manganese
compounds [108110]. This double-exchange interaction due to spin degrees of
freedom of Mn ions is the major premise for CMR. In order to shed light on the
interplay of the other degrees of freedom with the CMR, much research has been
performed so far. The charge degrees of freedom due to the doped Mn
4
ions in a sea
of Mn
3
ions has an interplay with the spin degrees of freedom by the double-
exchange mechanism. Furthermore, the doubly degenerate orbitals of Mn
3
ion
Figure 26. Ultrasonic dispersion of the longitudinal c
33
mode for Sr
12
Ca
2
Cu
24
O
41
:
(a) experimental results; (b) calculation with equation (22 a) and (22 b) [67].
exhibit frequently dierent types of orbital ordering, which brings about an
anisotropic character of the electron transfer for adjacent Mn ions. The fact that
the lattice degree of freedom is coupled to the orbital degree of freedom also plays a
role in the CMR owing to the dynamic JahnTeller mechanism [111]. The
competition among these dierent types of ordering of the 3d electron system
responsible for the metal-insulator transitions or the CMR has been reviewed by
Imada et al. [112].
In the cubic crystalline electric eld potential, the 3d
4
state of the trivalent
Mn
3
ion splits into a ground-state T
2g
triplet and an excited E
g
doublet at an
energy 10Dq % 2 eV. The ferromagnetic Hund rule coupling aligns S
1
2
of the E
g
doublet parallel to S
3
2
of the T
2g
triplet. The ferromagnetic order or the external
magnetic eld increases the transfer of the E
g
electron of the Mn
3
ion to the
neighbouring Mn
4
sites. The double-exchange interaction mediated by the E
g
electron stabilizes the ferromagnetic state in the doped sysem La
1x
Sr
x
MnO
3
instead
of the antiferromagnetism of the end material of LaMnO
3
. The increase in the
transfer integral t
ij
of E
g
electrons among neighbouring sites in the ferromagnetic
state is the main origin of the CMR or metalinsulator transition in the system.
Furthermore, the quadrupole (orbital) ordering and the charge ordering of the
doped Mn
4
ions considerably aect the transfer motion of an E
g
electron to
neighbouring sites.
The E
g
doublets are occupied by an electron with spin S
1
2
parallel to S
3
2
of
T
2g
. Because the direct product of E
g
is reduced as E
g
E
g
A
1g
A
2g
E
g
, the
quadrupoles of O
0
2
2l
2
z
l
2
x
l
2
y
3
p
and O
2
2
l
2
x
l
2
y
with E
g
symmetry and the
octupole T
xyz
with A
2g
are relevant for the E
g
doublet of Mn
3
ions in the
compounds La
1x
Sr
x
MnO
3
and Pr
1x
Ca
x
MnO
3
. Here l
x
. l
y
and l
z
are the angular
momentum components. The quadrupoles of O
0
2
and O
2
2
couple bilinearly to the
elastic strains
u
and
v
with the same symmetry as H
QS
g
3
O
0
2
u
O
2
2
v
. This
type of the quadrupolestrain coupling leads to the structural change associated with
the quadrupole ordering [112116]. The quadrupoles O
yz
. O
zx
and O
xy
with T
2g
symmetry, however, are absent for the E
g
doublet of Mn
3
ion in the present case.
As shown in gures 28 and 29, the elastic constant c
11
c
12
2 reveals a
Figure 27. Perovskite structure of the manganese oxides with R
1x
A
x
MnO
3
. Here R is a
trivalent rare-earth ion and A is a divalent alkaline ion. The charge due to the doped
Mn
4
ions in the Mn
3
-ion sea gives rise to charge ordering at low temperatures.
considerable softening above the structural transition T
s
290 K for La
1x
Sr
x
MnO
3
with x 0.12 and T
s
310 K for La
1x
Sr
x
MnO
3
with x 0.165, while the
associated c
44
mode shows a monotonic increase above T
s
[117]. The softening
c
11
c
12
2 above T
s
in both compounds is well tted by the formula
c
c
0
T T
0
c
T Y, which is deduced from the strain susceptibility .
3
responsible for O
0
2
O
2
2
of the E
g
doublet in Mn
3
. Here Y means the intersite
quadrupole interaction and T
0
c
is the critical temperature. The dierence between
two characteristic temperatures E
JT
T
0
c
Y 10N50 K indicates the JahnTeller
coupling energy of the system. See the discussion on equation (14). The spontaneous
tetragonal distortion h
u
i at the structural transition point of La
1x
Sr
x
MnO
3
with
x 0.12 is written for quadrupole ordering as h
u
i f2Ng
3
c
0
11
c
0
12
ghO
0
2
i.
The spontaneous strain estimated with this formula by Hazama et al. [117] is in
fairly good agreement with the elastic neutron measurements by Kawano et al. [118].
The direct observation of the orbital (quadrupole) ordering in the end material
LaMnO
3
has been achieved successfully for the rst time by resonant X-ray
scattering [19].
Figure 28. Temperature dependence of the elastic constants of La
1x
Sr
x
MnO
3
x 0.12N0.125. The softening of c
11
c
12
2 above the structural transition
T
s
290 K is well described by the formula c
c
0
T T
0
c
T Y due to the
quadrupolestrain coupling of Mn
3
ions. The transverse c
11
c
12
2 and c
44
modes
exhibit softening above the charge-ordering temperature T
co
145 K owing to Mn
4
ions in a Mn
3
-ion sea. Below the charge-ordering temperature T
co
, the echo signal
disappears owing to ultrasonic attenuation.
5.1.2. Charge ordering
The doped Mn
4
ions in the Mn
3
-ion sea exhibit charge ordering due to the
Coulomb interaction. The thermal hopping motion of 3d electrons from the E
g
orbital in Mn
3
to the neighbouring Mn
4
ions is relevant for the charge uctuation
of the system. The charge uctuation mode interacts with the lattice degree of
freedom. As shown in gure 29, the transverse modes of c
11
c
12
2 and c
44
for
La
1x
Sr
x
MnO
3
with x 0.12 exhibit considerable softening above the charge-
ordering point T
C
145 K. The ultrasonic echo signal disappears completely in the
charge-ordered state below T
C
for La
1x
Sr
x
MnO
3
with x 0.12 owing to the
scattering by monoclinic domain walls. Because the doped Mn
4
ions for
x 0.12N0.125 are proportionate to the lattice periodicity, charge ordering commen-
surable with the lattice is possible. The recent resonant X-ray scattering experiments
by Endoh et al. [119] on La
1x
Sr
x
MnO
3
x 0.12N0.125 signied the transition
driven by orbital ordering at T
C
145 K, which is subtly dierent from the charge-
ordering picture proposed by neutron scattering experiments [120] and elastic
constant measurements [121]. Nevertheless it is valuable to analyse the softening of
both c
11
c
12
2 and c
44
modes above T
C
by equation (14) of
c
c
0
T T
0
c
T Y. The characteristic temperatures T
0
c
150 K and
Y 142 K for the c
11
c
12
2 mode are considerably larger than T
0
c
134 K and
Y 132.5 K for the c
44
mode (see gure 29). This result indicates that the charge
uctuation mode with E
g
symmetry plays a predominant role in the charge ordering.
In the compound with x 0.165 in gure 30, however, the longitudinal c
11
and
the bulk modulus c
B
show a rounded minimum at the charge-ordering point
T
C
90 K. Furthermore, the transverse mode c
11
c
12
2 and c
44
modes for
x 0.165 have a small anomaly around T
C
. This elastic behaviour suggests that
Figure 29. Elastic softening of c
11
c
12
2 and c
44
above the charge-ordering temperature
T
co
145 K in La
1x
Sr
x
MnO
3
with x 0.12N0.125: (), ts with equation (14)
in the text.
the charge glass ordering of Mn
4
ions is realized for x 0.165 instead of the
freezing of the charge uctuation mode with symmetry-breaking character. The
disproportional ratio of Mn
4
to Mn
3
for the concentration x 0.165 favours the
charge glass state rather than charge ordering commensurable with the lattice
periodicity. In addition, the ferromagnetic transition at T
C
260 K for x 0.165
in gure 30 increases the carrier number dominated by E
g
electrons. The existence of
the carriers is also important for the charge glass state for x 0.165.
5.2. Pr
1x
Ca
x
MnO
3
and Nd
0.5
Sr
0.5
MnO
3
Charge ordering of the doped Mn
4
ions in the Mn
3
-ion sea in Pr
1x
Ca
x
MnO
3
0.35 < x < 0.5 is important for the manifestation of the CMR [107]. The charge-
ordered state in zero magnetic eld is characterized as being an insulator with
increasing resistivity on lowering the temperature. The transfer integral t
ij
of
electrons of Mn
3
ions to the Mn
4
ions with parallel spin direction at neighbouring
sites increases in applied magnetic elds because of the ferromagnetic Hund rule
coupling and the double-exchange mechanism. In magnetic elds, the kinetic energy
due to the transfer integral providing the ferromagnetic metallic state becomes
superior to the Coulomb interaction among Mn
4
ions and Mn
3
ions, which
favours an insulator state. Many theoretical studies dealing with the competition
Figure 30. Temperature dependence of the elastic constants of La
1x
Sr
x
MnO
3
x 0.165.
The softening of c
11
c
12
2 above the structural transition T
s
310 K is well
described by the formula c
c
0
T T
0
c
T Y due to the quadrupolestrain
coupling of Mn
3
ions. The rounded dip around T
co
90 K indicates charge glass
order in the system.
between the ferromagnetic and charge-orbital ordered phases have been reported
[122124]. Consequently, in magnetic elds the insulator phase turns into the
metallic phase, where the ordered charge lattice state melts into the disordered
charge liquid state. This is the main scenario for the eld-induced metalinsulator
transition in Pr
1x
Ca
x
MnO
3
. It is interesting to note that the orbital ordering of
O
0
2
or O
2
s
of Mn
3
ions aects the anisotropic character of the transfer t
ij
of E
g
electrons.
Charge ordering in the compound with x 0.50 in the ratio NMn
4
:
NMn
3
1 : 1 is representative of the system because the charge population of
the doped Mn
4
ions is proportional to the lattice periodicity. The depopulation in
the ratio of Mn
3
to Mn
4
of under-doped compounds (x 0.40 and 0.35) makes
charge ordering less stable. The elastic constants of Pr
1x
Ca
x
MnO
3
x 0.50 in
gure 31 show step anomalies at the charge-ordering point T
C
220 K. The relative
change in the elastic constants of c
11
c
12
2 and c
44
of the compounds with
x 0.50, 0.40 and 0.35 are also shown in gure 32. The softening of the c
11
c
12
2
mode below about 400 K down to T
C
in gure 32 is due to the coupling to the
quadrupole moment O
0
2
or O
2
2
of the E
g
doublet of Mn
3
ions [121]. This point was
discussed for La
1x
Sr
x
MnO
3
in the previous section 5.1.
The softening of c
44
in the vicinity of the charge-ordering point T
C
in gure 32,
however, originates from the coupling to the charge uctuation mode of the system.
In order to take into account the coexistence of dierent valence ions in the ratio
NMn
4
: NMn
3
1 : 1, we introduce an extended unit cell consisting of the
eight molecules, where charge neutrality is satised. The extended unit cell has the
11
, c
11
c
12
2, c
44
and c
B
in Pr
1x
Ca
x
MnO
3
with x 0.50.
cubic symmetry O
h
. Applying the theory presented in section 2.1 for the charge
distribution of eight Mn ions in the extended unit cell, the charge uctuation mode
with eight dimensions reduces to the direct sum of the irreducible representations as
A
1g
1d A
2u
1d T
1u
3d T
2g
3d. The projection operator of equation (7)
provides the charge uctuation mode in table 13. The charge neutrality over
the extended unit cell constrains the charge distribution in the extended unit cell.
The j
A
1g
value with full symmetry possesses a uniform distribution of fractional
charge 3.5e for each Mn site. The charge uctuation modes j
A
2u
. j
T
1u
and j
T
2g
with
11
c
12
2 and c
44
around
the charge-ordering transition temperature T
co
220N230 K in Pr
1x
Ca
x
MnO
3
with
x 0.35, 0.40 and 0.50.
Table 13. The charge uctuation mode for the extended unit cell consisting of eight molecules
of Pr
1x
Ca
x
MnO
3
.
1
A
1g
j
A
1g
j
1
j
2
j
3
j
4
j
5
j
6
j
7
j
8

B

xx
yy
zz
2
A
1u
j
A
2u
j
1
j
2
j
3
j
4
j
5
j
6
j
7
j
8
3
E
g

u
2
zz
xx
yy
3
p
v

xx
yy
4
T
1u
j
T
1u
.x
j
1
j
2
j
3
j
4
j
5
j
6
j
7
j
8
j
T
1u
.y
j
1
j
2
j
3
j
4
j
5
j
6
j
7
j
8
j
T
1u
.z
j
1
j
2
j
3
j
4
j
5
j
6
j
7
j
8
5
T
2g
j
T
2g
.yz
j
1
j
2
j
3
j
4
j
5
j
6
j
7
j
8
j
T
2g
.zx
j
1
j
2
j
3
j
4
j
5
j
6
j
7
j
8
j
T
2g
.xy
j
1
j
2
j
3
j
4
j
5
j
6
j
7
j
8
yz
zx
xy
symmetry-breaking character consists of the integer valence 3e or 4e for Mn sites.
The softening of the c
44
mode in gure 32 results from the coupling to the charge
uctuation modes j
T
2g
.yz
. j
T
2g
.zx
and j
T
2g
.xy
in table 13. These charge distributions of
the T
2g
triplet are presented in gure 33.
Taking into account the free-energy equation (20) consisting of power series of
the order parameters Q
yz
. Q
zx
and Q
xy
for the T
2g
triplet, we obtain three types of
solution for the charge-ordered state. Case (i) with Q
xy
6 0 and Q
yz
Q
zx
0,
corresponds to charge order with an alternate arrangement of Mn
3
and Mn
4
ions
with unit charge, which results from the freezing of the charge uctuation mode
j
T
2g
.xy
in table 13 below T
C
. The other two cases, namely case (ii) with Q
yz
Q
zx
6 0
and Q
xy
0 and case (iii) with Q
yz
Q
zx
Q
xy
6 0, lead to fractional charge
disributions, which are not responsible for the ordered state. Because of the absence
of the charge uctuation mode of E
g
symmetry in table 13, the softening of the
c
11
c
12
2 in gure 32 is mainly accounted for by the coupling to the quadrupole
moment O
0
2
and O
2
2
of Mn
3
ions. It is remarkable that the charge uctuation mode
of T
2g
couples to the c
44
mode and the orbital uctuation mode of E
g
couples to the
c
11
c
12
2 mode. This result signies that the elastic constant is a favourable probe
for characterizing the charge as well as orbital states in Pr
1x
Ca
x
MnO
3
. In spite of
the random distribution of trivalent rare-earth Pr ions and divalent alkali-metal Ca
ions over the crystal, distinct charge ordering with a symmetry-breaking character is
realized in Pr
1x
Ca
x
MnO
3
. The fact that the interactions between 3d electrons of Mn
ions are superior to the disorder eect due to random potential is an important
feature of the strongly correlated electron systems treated here.
The charge-ordering pattern of Q
xy
6 0, Q
yz
Q
zx
0, corresponds to one of
the orderings anticipated in the work on the isostructural compound [La,M(II)]
MnO
3
by Goodenough [125]. The magnetic neutron scattering showed already that
Mn
3
and Mn
4
ions with dierent magnetic moments are arranged alternately in
the ab plane and are parallel to the c direction [126]. The resonant X-ray scattering
on Pr
1x
Ca
x
MnO
3
(x 0.40 and 0.50) revealed charge order of the alternate
arrangement in the ab plane accompanied by orbital ordering of O
0
2
as well [127].
A brief study of longitudinal sound velocity measurements in a related
compound Nd
0.5
Sr
0.5
MnO
3
resulted in a strong hardening of the elastic mode at
the chargeorbital-order transition temperature T
C
145 K [128]. With applied
magnetic elds a BT phase diagram was mapped, using ultrasonic and magnetiza-
Figure 33. Charge uctuation mode j
T
2g
.yz
. j
T
2g
.zx
. j
T
2g
.xy
. of Mn
3
and Mn
4
ions in the Mn
compound Pr
1x
Ca
x
MnO
3
with x 0.50. One of the three modes freezes below T
co
(see table 13).
tion measurements, which gave strong hysteresis due to the rst-order metal
insulator phase transition.
The microstructure in charge ordering of Pr
1x
Ca
x
MnO
3
observed by the
electron microscopy revealed competition between orbital and charge degrees of
freedom [129]. Phase separation consisting of the ferromagnetic metallic phase and
the charge-ordered insulator phase has been found in (La
1z
Nd
z
)
1x
Ca
x
MnO
3
by
controlling the amount of doping [130]. An applied magnetic eld increases the
ferromagnetic metallic part in the composite. The CMR may result from inter-
connection among the ferromagnetic part in magnetic elds [131].
5. Conclusion and outlook
We have given a survey on charge-ordering phenomena as they occur in many
solid-state compounds consisting of 3d or 4f electrons. We investigated such diverse
systems as Yb
4
As
3
, Fe
3
O
4
, NaV
2
O
5
, Sm
3
Te
4
and Sr
14
Cu
24
O
41
and the doped
systems La
1x
Sr
x
MnO
3
and Pr
1x
Ca
x
MnO
3
. These substances exhibit so-called
inhomogeneous valence eects, and in some cases charge orderings due to Coulomb
interaction or a charge glass state due to frustration eect.
We concentrated mainly on lattice eects occurring at charge-order transitions,
that is structural eects determined by X-ray or elastic neutron scattering and the
temperature dependence of symmetry elastic constants. The latter quantity gives the
strain susceptibility, that is the response of the order parameter to an applied
dynamic strain of the ultrasonic wave. In some favourable cases this quantity causes
soft-mode behaviour, which leads to the frozen mode as the order parameter in the
charge-ordered phase.
The Landau theory for phase transitions was used to analyse the symmetry
aspects of the charge uctuation modes and the temperature dependence of the
symmetry elastic constants. The experimental observation of soft elastic modes is an
excellent guide to predict the charge uctuation mode freezing at the charge-ordered
phase. This was particularly successful for describing the charge ordering in Yb
4
As
3
,
magnetite, NaV
2
O
5
and Pr
1x
Ca
x
MnO
3
(x 0.5). The frequency dependence of the
elastic constants and ultrasonic attenuation describes the dynamics of thermal
hopping processes of valence electrons between ions with dierent valences. A
comparison between Sm
3
Se
4
and Eu
3
S
4
gave qualitative clues of the subtle
dierences between a transition to a charge glass state and a charge-ordered state.
The low-temperature decrease of elastic constants with ln T dependence in Sm
3
Te
4
characterizes the two-level system due to tunnelling of 4f electrons in the charge
glass state.
A microscopic description of these phenomena, such as charge ordering and the
charge glass state, is completely lacking. First attempts were made to gain some
insight into the various ground states from calculation of the Madelung energy of the
assembly of charged ions, but screening eects and hybridization eects, as well as
the interplay with magnetic and orbital eects, should also produce important
contributions. With this experimentally and symmetry-oriented review, we hope to
stimulate detailed model calculations.
Acknowledgements
Stimulating discussions with Dr Y. Nemoto and Dr H. Schwenk are gratefully
acknowledged. This work was partly supported by a grant-in-aid from the Ministry
of Education, Culture, Sports, Science and Technology of Japan. Support by the
invited fellowship program for research in Japan of the Japan Society for the
Promotion of Science is gratefully acknowledged.
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Charge ordering, charge uctuations and lattice eects in strongly

correlated electron systems

0 in the disordered phase above T

6 0 in the charge-ordered phase below T

!1. In order to elucidate the

consisting of the charge uctuation modes as [17]

is the number of irreducible representations , which is contained in the

s is the character of the irreducible representation in G

of the irreducible representation

upon the base of the charge uctuation

is the dimension of the irreducible representation . D

s for the symmetry operator s. Useful

induced by the transverse ultrasonic wave couples to the charge uctuation

is a coupling constant between the order parameter Q

for the charge

and the elastic strain

. For the description of the

is the transition temperature with c

for the bases with the same

. In this process, group-theoretical techniques are

s of the irreducible representations for the space group T

of the irreducible representations is obtained

consisting of the linear combinations of the charge densities j

for the appropriate bases.

s is the character of the irreducible representation.

of the irreducible representation in Yb

0 124 27.2 17.8 6.1

T. Goto and B. Luthi 90

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