Quantum Theory of Multiferroic Helimagnets: Collinear and Helical Phases

Hosho Katsura,
1
Shigeki Onoda,
2
Jung Hoon Han,
3
and Naoto Nagaosa
1,4
1
Department of Applied Physics, The University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
2
Condensed Matter Theory Laboratory, RIKEN, Wako, Saitama 351-0198, Japan
3
BK21 Physics Research Division, Department of Physics, Sungkyunkwan University, Suwon 440-746, Korea
4
Cross Correlated Materials Research Group, Frontier Research System, Riken,2-1 Hirosawa, Wako, Saitama 351-0198, Japan
(Received 2 April 2008; published 31 October 2008)
We study the quantum uctuation in the cycloidal helical magnet in terms of the Schwinger boson
approach. In sharp contrast to the classical uctuation, the quantum uctuation is collinear in nature which
gives rise to the collinear spin density wave state slightly above the helical cycloidal state as the
temperature is lowered. Physical properties such as the reduced elliptic ratio of the spiral, the neutron
scattering and infrared absorption spectra are discussed from this viewpoint with the possible relevance to
the quasi-one dimensional LiCu
2
O
2
and LiCuVO
4
.
DOI: 10.1103/PhysRevLett.101.187207 PACS numbers: 75.80.+q, 71.70.Ej, 75.30.Kz, 77.80.e
Frustration, competition between interactions, in mag-
nets has been an intriguing issue in the eld of classical/
quantum magnetism over several decades. In the usual
case, even with the competing exchange interactions
1
|]
s, their Fourier transform 1q has the maximum at
some wave vector q Q, and the classical ground state
becomes the helimagnet [1]. This is because of the con-
straint on the length of the classical spin, i.e., jS
]
j fixed.
In strongly frustrated quantum magnets, on the other hand,
the long-range order is possibly destroyed, and novel
ground states without magnetic order may be realized.
Many possibilities such as chiral spin liquid [2], spin-
nematic [3], and spin-Peierls/valence-bond-crystal [4]
states are theoretically proposed. Another possibility is a
magnetically ordered state realized by the order-by-
disorder mechanism [5].
Recently, a renewed interest has been focused on the
cycloidal helimagnets from the viewpoint of multiferroics,
which exhibit both magnetic and ferroelectric properties
[6,7]. These materials shed some new light on the frus-
trated magnets since the electric polarization is closely re-
lated to the vector spin chirality S
|
S
]
[812]. Namely, it
was found that the electric polarization (P) produced by the
neighboring spins (S
|
and S
]
) can be written as
P oe
|]
S
|
S
]
, (1)
where e
|]
denotes the unit vector connecting the sites | and
]. This relation has a physical interpretation in terms of
spin current induced between noncollinear spins due to
frustration [8].
Magnetic materials with the nite vector spin chirality
include a wide range of systems such as three dimensional
(3D) magnets RMnO
3
(R Gd, Tb, Dy) with spin S 2
[1316], the kagome staircase compound Ni
3
V
2
O
8
with
S 1 [17], S 1,2 quantum spin chains LiCu
2
O
2
[18,19], LiCuVO
4
[20], and the quasi-one-dimensional
(1D) molecular helimagnet with S 7,2 [21].
Depending on the temperature, dimensionality, and mag-
nitude of the spin S, the role of the classical/quantum spin
uctuations differs, and the theoretical studies on these
uctuations are needed for the consistent interpretation of
the phase diagram and the physical properties of these
systems. Especially, the low dimensionality enhances
both thermal and quantum uctuations leading to the
breakdown of the conventional semiclassical picture for
helimagnets. The possible chiral spin states without mag-
netic long-range order have been proposed theoretically for
classical [2224] and quantum [2527] spin systems.
However, the systematic study of the quantum uctuation
in the helimagnets including the nite temperature effect is
rare, which is addressed in this Letter and will be comple-
mentary to the works mentioned above.
In this Letter, we study the quantum/thermal uctuation
in the helimagnet in terms of the Schwinger boson (SB)
approach [28]. The advantage of the SB method is that it
can describe the length of the ordered moment as a soft
variable. Namely, in the constraint on the Schwinger boson
number at each site,
P
a
l
y
]a
l
]a
2S, it can be decom-
posed into the condensed (classical) part and the uctuat-
ing part. In the SB language, the paramagnetic-to-collinear
transition is described by the density wave instability of
bosons, while the collinear to helical one corresponds to
the Bose-Einstein condensation (BEC) of SB.
Effective model.We study quasi-1D and two-
dimensional (2D) Heisenberg models with the exchange
interactions shown in Fig. 1, where 1
1
is ferromagnetic,
while 1
2
is antiferromagnetic, leading to the frustration.
The interchain/interplane interaction 1
?
is assumed to be
sufciently weak. The spin-S operators are represented by
SB as S
n
l
y
a
a
n
aa
0
,2l
a
0 , where a
n
(n x, y, z) are the
Pauli matrices and the repeated indices are summed over.
First, we assume that the resonating-valence-bond (RVB)
correlation is dominant and neglect the other mean-eld
decoupling. This assumption is valid for the low-
dimensional multiferroics such as LiCuVO
4
[20], LiCu
2
O
2
[18], and Ni
3
V
2
O
8
[17]. The mean-eld Hamiltonian of the
PRL 101, 187207 (2008)
P HYS I CAL RE VI E W L E T T E RS
week ending
31 OCTOBER 2008
0031-9007,08,101(18),187207(4) 187207-1 2008 The American Physical Society
quasi-1D model is given by
H
MF
q1D

X
ka
2,
1
cosk
x
l
y
ka
l
ka

X
k
2,
2
sin2k
x
,
?
sink
y
sink
z
l
y
k"
l
y
k#
h.c. 2N,
2
1
,1
1
,
2
2
,1
2
2,
2
?
,1
?
S,
(2)
where N is the total number of sites and l
ka
is the Fourier
transform dened by l
]a

P
k
e
|kR
]
l
ka
,

N
p
. In H
MF
q1D
,
denotes the chemical potential for the bosons and the
order parameters ,
1
, ,
2
, and ,
?
are 1
1
hl
y
|a
l
|^ x,a
i,2,
1
2
hl
|:
e
:a
l
|2^ x,a
i,2|, and 1
?
hl
|:
e
:a
l
|^ e,a
i,2| ( ^ e ^ y,
^ z), respectively, with e
#"
e
"#
1. RVB order parame-
ters are assumed to be real and spatially uniform. In a
parallel way, we can derive the quasi-2D mean-eld
Hamiltonian H
MF
q2D
. The Hamiltonian H
MF
q1D
can be diago-
nalized by the Bogoliubov transformation as H
MF
q1D

P
ka
wk
y
ka

ka
1,2 const, with the dispersion re-
lation wk
2
2,
1
cosk
x

2
2,
2
sin2k
x

2,
?
sink
y
sink
z

2
. The chemical potential is deter-
mined by the condition on the boson number. ,s are
obtained by minimizing the mean-eld free energy.
Figure 2 shows the numerically obtained ,
1
, ,
2
and the
gap T wQ,2 of the 1D spin-1,2 model as a func-
tion of 1
1
,1
2
. In the calculation, 1
?
is assumed to be small,
and ,
?
is set to zero [29]. We have also numerically
studied the 2D model at nite temperature and obtained
similar results. From ,s, we can estimate the minima of
the dispersion wk as Q,2 Q,2, r,2, r,2. Q is
determined to satisfy 2,
1
cosQ,2,
1
sinQ,2
4,
2
sinQ 2,
?
,
2
cosQ.
To describe the low-energy physics of the model, it is
useful to construct an effective continuum model. First, we
suppose that ,s are nonzero. Next, we expand the disper-
sion around the minima up to quadratic order in k Q,2.
The effective dispersion relations of -particles are those
of massive relativistic bosons and explicitly given by
k

T
2
c
2
k
jk
k
j
2
c
2
?
jk
?
j
2
q
, where k
k
is the
vector along (within) the chain (plane) while k
?
is that
perpendicular to the chain (plane). The spin wave veloci-
ties c
k
and c
?
can be written in terms of ,s, in principle.
Now the effective Hamiltonian of our system is
H
eff

X
ka
X
n
k
y
kan

kan
1,2, (3)
where n () indicates that the momentum is around
Q,2 (Q,2). When the gap T wQ,2 vanishes,
s are the linear dispersions of the Goldstone modes.
Collinear phase.To study the instability toward mag-
netic ordering, we consider the mean-eld decoupling of
the interchain/interplane interaction corresponding to the
density wave formation of the SB [30,31]. The total
Hamiltonian is given by H
q1D,q2D
H
MF
q1D,q2D
H
int
with
H
int
z1
?
fNja |bj
2

N
p
a |b S
Q
h.c.g,
where z is the coordination number along interchain/
interplane direction and a and b are mean elds de-
ned through hS
Q
i

N
p
a |b with S
Q

P
k
l
y
kQ,a

aa
0 ,2l
ka
0 ,

N
p
. Small ,
?
or c
?
does not
change the following results, and hence, we put ,
?
0 in
Eq. (4). The collinear and helical orders are expressed as
a b 0 and a b 0, respectively [24]. The interac-
tion between -bosons is enhanced near the bottom of the
dispersion inversely proportional to the gap T in Fig. 3
(a). It inevitably leads to the density wave instability before
the occurrence of BEC. From the rotational symmetry in
spin space, we can set o
z
l
z
0 without loss of general-
ity. By introducing x z1
?
jo
x
|o
y
|l
x
|l
y
j and
y z1
?
jo
x
|o
y
|l
x
|l
y
j, the free-energy den-
sity corresponding to the Hamiltonian H
q1D,q2D
can be
written in a decoupled form: ]x
2
]y
2
[32]. From
the fact that a b / x
2
y
2
, the collinear phase appears
if ]x
2
has a global minimum at x
2
0. In the quasi-1D
case, ]x
2
]0 can be expanded as Ax
2
Bx
4
with
A
1
T

T
2z1
?

S 1,2
8uT

,
B
1
T
3

S
1
2

uT
3
128

9
1 2uT
2
,3
2
1 uT
2
5

,
(4)
FIG. 2 (color online). RVB order parameters ,
1
and ,
2
, and
the gap of the S 1,2 1D model with varying 1
1
,1
2
at zero
temperature. Inset shows the temperature dependence of ,
1
and
,
2
at 1
1
,1
2
0.5. We use the unit 1
2
k
B
1. The transition
temperature is given by T
RVB
1
2
S 1,2, ln1 1,S.
) (b x
) (c y
) (a z
2
J
1
J
1
J
2
J
(b) (a)
FIG. 1 (color online). Schematic lattice structure and exchange
interactions of the effective spin model. 1
1
is ferromagnetic,
while 1
2
is antiferromagnetic. xyz-coordinates and olc-axes are
also shown.
PRL 101, 187207 (2008)
P HYS I CAL RE VI E W L E T T E RS
week ending
31 OCTOBER 2008
187207-2
where uT T,
~
T (
~
T 2,
1
cosQ,2) is
the normalized gap. Here, we have assumed T ) T.
Since B is positive for 0 < uT <1, a sufcient condition
for the collinear phase is A < 0, and a second order phase
transition to the collinear state occurs at A 0. Above
T
RVB
, uT $ 1 and hence the inequality A < 0 is not
satised for small z1
?
. This means T
N
<T
RVB
, where T
N
is the antiferromagnetic transition temperature. Further
lowering the temperature with increasing x, the gap col-
lapses to result in BEC of SB. Therefore, we conclude
T
BEC
< T
N
<T
RVB
. In this way, the instability towards the
collinear order is a robust feature of the strongly uctuating
quantum helimagnets, and is essentially different from that
of classical system with an easy axis anisotropy. Now, we
describe the collinear state a b 0, o
y
, 0 where the
4-fold degeneracy for the energy of
kan
is split into upper
and lower branch bands [see Fig. 3(b)]. The lower-branch
band consisting of n
k
and
k
which are linear combina-
tions of
kan
is 2-fold degenerate [32]. Below, we will
focus on the low energy dynamics, and neglect the
upper-branch bosons. This leads to the relation between
the original bosons l
ka
: l
Q,2k"
$ e
|r,4
l
Q,2k#
and
l
y
Q,2k#
$ e
|r,4
l
y
Q,2k"
.
Helical phase.Next, we consider the BEC of the low-
est modes n
0
and
0
caused by the nite ,
?
. This corre-
sponds to the nonzero expectation values of l
Q,2,a
. We
obtain the cycloidal helical spin structure as
S
l
|
$ sinQ R
|
r,4jhl
Q,2"
ij
2
jhl
Q,2#
ij
2
,N,
S
c
I
$ ScosQ R
I
r,4,
S
o
I
$ sinQ R
I
r,4hl
Q,2"
ihl
Q,2#
i c.c.,N. (5)
Here, we have used the relaxed constraint
P
|a
l
y
|a
l
|a

2SN. Now, we clarify the relation between the elliptic
ratio and the Bose condensate fraction. If we assume that
hl
Q,2#
i 0 while hl
Q,2"
i 0, S
o
|
becomes zero and the
elliptic ratio is given by m
l
,m
c
$ jhl
Q,2"
ij
2
,NS. In this
case, the spins are rotating counterclockwise within the
lc-plane. The clockwise helicity is realized when
hl
Q,2"
i 0 while hl
Q,2#
i 0. Note that the elliptic ratio
can be much smaller than unity even at zero temperature
due to the strong quantum uctuation in sharp contrast to
the classical case where higher harmonics are needed.
Neutron scattering.We shall focus on the quasi-1D
case with the possible relevance to the recent experiment
in the helical phase of LiCu
2
O
2
[19]. Henceforth, we set
hl
Q,2"
i 0 and hl
Q,2#
i 0 to take one of the helicities.
The spin correlations I

q hS

Qq
S

Qq
i and
I
nn
q hS
n
Qq
S
n
Qq
i (n x, y) were observed with
S
n
ko-axis and S
n
kc-axis congurations, respectively,
where S
n
is the neutron spin [19]. Let us examine them
in terms of SB theory. We rst consider the Bragg compo-
nent, i.e., q 0 and w 0 component. Using the Fourier
transforms of Eq. (5), we obtain I

0 NS
2
1
r
2
,4 while I
xx
0 I
yy
0 NS
2
1 r
2
,4, where
r jhl
Q,2"
ij
2
,NS. Next, we consider the non-Bragg
part, i.e., nonzero q component contributing to the scatter-
ing intensity due to the nite energy window. In the energy
regime where the continuum model is valid, using n
k
and

k
, one can show that I

q E
1
q E
2
q and
I

q E
2
q with
E
1
q rS

S
1
2

2c
k
T
c
2
k
q
2
c
2
?
jq
?
j
2
,
E
2
q $

S
1
2

2
T
2
16c
2
?
1
q
,
where q is the x component of q. The E
1
term is directly
related to the condensate fraction while the common E
2
term exists even when r 0. On the other hand, one can
show that I
xx
q I
yy
q E
1
q,2 E
2
q for q 0.
The interchain interaction 1
?
can be estimated from the
transition temperature T
N
as T
N
/ 1
?
[31,33]. For
LiCu
2
O
2
, T
N
24.5 K and assuming z 4, we obtain
1
?
$ 8 K. The exchange interactions along the chain are
estimated as j1
1
j 11 meV and 1
2
7 meV [18], and the
ratio of the velocities c
?
,c
k
$1
?
,1
k
$ 10
1
. The mea-
surement was performed at 7 K [19] which is of the same
order as 1
?
, and hence T
3
,1
k
1
2
?
$T,1
k
. Therefore, the
thermally excited uctuations are quasi-one dimensional at
T 7 K, and the collinear magnetic order parameter is
still small. This further enhances the importance of the
quasielastic contribution to the Bragg intensity and may
resolve the puzzle of I
xx
$I
yy
and jI

j (
I

[19,27]. In order to extract the information

on the Bragg component exclusively, one needs to cool
down the temperature to T ( 1
?
.
Dielectric response.Finally, we examine the dynami-
cal dielectric response both in the paramagnetic and heli-
cal phases of the quasi-1D model. We assume that the
uctuating electric polarization is given by Eq. (1). We
take the mean-eld decoupling S
|
S
]
hl
y
|
l
]
i
l
y
]

:
l
|:
h.c.,4| to the ferromagnetic bonds and
S
|
S
]
hl
y
|
e

l
y
]
il
]a

a
e
:
l
|:
h.c.,4| to
the antiferromagnetic bonds. We henceforth focus on the
contribution from the antiferromagnetic (1
2
) bonds since
a)
2 / / Q 2 Q
Q
b)
k
Goldstone
2-fold
2-fold
2-fold
k k
(T)
c)
) , (
2-fold
Amplitude
2-fold
Q
FIG. 3 (color online). (a) Schematic energy dispersion of
-particles. Minima are at k Q,2. (b) The reorganization
of the SB due to the collinear magnetic order. The origin of the
momentum k is shifted by Q,2. (c) Goldstone and amplitude
modes associated with the BEC in the helical phase.
PRL 101, 187207 (2008)
P HYS I CAL RE VI E W L E T T E RS
week ending
31 OCTOBER 2008
187207-3
its uctuation is stronger than that of the ferromagnetic
one. From the geometry of the system (see Fig. 1), the
polarization along the l-axis P
l
is always zero. In the
paramagnetic phase, Ims
oo
w Ims
cc
w due to the ro-
tational symmetry in spin space. The expression for the
polarization along the o-axis P
o
is given by
P
o
/ ,
2
,1
2

X
k
cos2k
x
|l
ka
l
ka
h.c..
The purely 1D result is shown in Fig. 4. Near the threshold
of the absorption, Ims
oo
w /

w 2T
p
before the
onset of ,
1
. On the other hand, a drastic change of the
absorption spectra occurs in the helical phase since the
low-lying branch bosons become gapless [see Fig. 3(c)]. In
this phase, the energy dispersions of the upper and lower
branches are given by

k
x

c
2
k
k
2
x
20
2
q
and

k
x
c
k
k
x
, respectively. We assume the BEC of SB
by the weak interchain interaction. The behavior at zero
temperature is shown in Fig. 4. There are three contribu-
tions corresponding to the processes of two bosons (i) in
the upper branch, (ii) in the gapless lower branch, and
(iii) in both the upper and lower branches, respectively.
Finally, it should be noted that there is also the one-magnon
contribution discussed in [34] which is, however, much
smaller in the limit of weak interchain interaction.
To conclude, we have studied the phase diagram and the
dynamical properties of quasi-low dimensional helimag-
nets. The collinear phase at slightly higher temperature
than the helical phase and the reduced elliptic ratio of the
spiral are realized by the quantum uctuation and the low
dimensionality. It is also shown that the polarized neutron
scattering and infrared absorption in quasi-1D helimagnets
reect the quantum uctuation.
The authors are grateful to S. Seki, Y. Yamasaki,
N. Kida, S. Todo, and Y. Tokura for fruitful discussions.
This work was supported in part by Grant-in-Aids (Grant
Nos. 15104006, 16076205, 17105002, 19048008,
19048010, and 20046016) and NAREGI Nanoscience
Project from the MEXT. H. K. was supported by the
Grant-in-Aid for JSPS (No. 1811271).
[1] A. Yoshimori, J. Phys. Soc. Jpn. 14, 807 (1959).
[2] V. Kalmeyer and R. B. Laughlin, Phys. Rev. Lett. 59, 2095
(1987); X.-G. Wen, F. Wilczek, and A. Zee, Phys. Rev. B
39, 11413 (1989).
[3] P. Chandra, P. Coleman, and A. I. Larkin, J. Phys.
Condens. Matter 2, 7933 (1990).
[4] N. Read and S. Sachdev, Phys. Rev. Lett. 66, 1773 (1991).
[5] C. L. Henley, Phys. Rev. Lett. 62, 2056 (1989).
[6] M. Fiebig, J. Phys. D 38, R123 (2005).
[7] Y. Tokura, Science 312, 1481 (2006).
[8] H. Katsura, N. Nagaosa, and A. V. Balatsky, Phys. Rev.
Lett. 95, 057205 (2005).
[9] I. A. Sergienko and E. Dagotto, Phys. Rev. B 73, 094434
(2006).
[10] C. Jia et al., Phys. Rev. B 76, 144424 (2007).
[11] M. Mostovoy, Phys. Rev. Lett. 96, 067601 (2006).
[12] A. B. Harris, Phys. Rev. B 76, 054447 (2007).
[13] T. Kimura et al., Nature (London) 426, 55 (2003).
[14] T. Goto et al., Phys. Rev. Lett. 92, 257201 (2004).
[15] K. Noda et al., J. Appl. Phys. 97, 10C103 (2005).
[16] M. Kenzelmann et al., Phys. Rev. Lett. 95, 087206 (2005).
[17] G. Lawes et al., Phys. Rev. Lett. 95, 087205 (2005).
[18] S. Park et al., Phys. Rev. Lett. 98, 057601 (2007).
[19] S. Seki et al., Phys. Rev. Lett. 100, 127201 (2008).
[20] Y. Naito et al., J. Phys. Soc. Jpn. 76, 023708 (2007).
[21] F. Cinti et al., Phys. Rev. Lett. 100, 057203 (2008).
[22] J. Villain, J. Phys. C 10, 4793 (1977).
[23] S. Miyashita and H. Shiba, J. Phys. Soc. Jpn. 53, 1145
(1984).
[24] S. Onoda and N. Nagaosa, Phys. Rev. Lett. 99, 027206
(2007).
[25] A. A. Nersesyan, A. O. Gogolin, and F. H. L. Essler, Phys.
Rev. Lett. 81, 910 (1998).
[26] T. Hikihara et al., J. Phys. Soc. Jpn. 69, 259 (2000).
[27] S. Furukawa et al., arXiv:0802.3256.
[28] A. Auerbach, Interacting Electrons and Quantum
Magnetism (Springer, New York, 1998).
[29] With moderate 3D couplings, our SB mean-eld theory
can give the helical magnetism even in quasi-1D half-
integer spin systems.
[30] D. J. Scalapino, Y. Imry, and P. Pincus, Phys. Rev. B 11,
2042 (1975).
[31] H. J. Schulz, Phys. Rev. Lett. 77, 2790 (1996).
[32] See EPAPS Document No. E-PRLTAO-101-054844 for
detailed derivations and discussions. There is also a de-
tailed comparison between our results and Ref. [27]. For
more information on EPAPS, see http://www.aip.org/
pubservs/epaps.html.
[33] C. Yasuda et al., Phys. Rev. Lett. 94, 217201 (2005).
[34] H. Katsura, A. V. Balatsky, and N. Nagaosa, Phys. Rev.
Lett. 98, 027203 (2007).
FIG. 4 (color online). Im e
oo
w in the paramagnetic phase
with T 0.8 (red/right), T 0.35 (green/middle), and the hel-
ical phase with T 0 (blue/left,
~


2
p
0). We take 1
1

0.25 and 1
2
1. The inset shows the enlargement of the low-
frequency region. Singularities are smeared out by the interchain
interaction as shown by the black lines. Behaviors near thresh-
olds are also indicated. Closed-form expressions for Ims
oo
w
are provided in [32].
PRL 101, 187207 (2008)
P HYS I CAL RE VI E W L E T T E RS
week ending
31 OCTOBER 2008
187207-4