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Charge Ordering in Half-Doped Manganites: Weak Charge Disproportion and

Leading Mechanisms

Dmitri Volja,1, 2 Wei-Guo Yin,1 and Wei Ku1, 2


1
Condensed Matter Physics & Materials Science Department,
Brookhaven National Laboratory, Upton, NY 11973
2
Physics Department, State University of New York, Stony Brook, NY 11790
(Dated: Received February 1, 2008)
The current puzzle of weak charge disproportion experimentally observed in half-doped
manganites—which has long been interpreted in the picture of strong Mn3+ /Mn4+ charge/orbital
arXiv:0704.1834v1 [cond-mat.str-el] 16 Apr 2007

order—is resolved by a novel Wannier states analysis of the LDA+U electronic structure. Strong
electron itinerancy in this charge-transfer system significantly delocalizes the occupied low-energy
“Mn3+ ” states such that charge leaks into the Mn4+ -sites. Based on a realistic effective Hamiltonian
derived from first-principles calculations, we further quantify the leading mechanisms of the charge-
orbital orders and find that both electron-lattice and electron-electron interactions are important.

PACS numbers: 75.47.Lx, 71.45.Lr, 71.10.Fd, 71.30.+h

The exploration of interplay among distinct orders lies actions in comparison with the well-accepted electron-
in the heart of condensed matter physics and materials lattice (e-l) interactions. For example, ∆n, the differ-
science, as this interplay often give rises to tunable prop- ence in the electron occupation number between Mn3+
erties of practical applications, such as exotic states and and Mn4+ states, was shown to be small in an e-e only
colossal responses to external stimuli. Manganese oxides picture [16]; this is however insufficient to explain the
such as La1−x Cax MnO3 , which host rich charge, orbital, observed small CD, since the established e-l interactions
spin, and lattice degrees of freedom, have thus attracted will cause a large ∆n [17]. Moreover, despite the common
great attention [1]. The vastly interesting colossal mag- belief that e-l interactions dominate the general physics
netoresistance (CMR) effect, found in some doping range of eg electrons in the manganites [5, 18], a recent the-
(x ∼ 0.2−0.4), is a good example of rich physics originat- oretical study [19] showed that e-e interaction plays an
ing from proximity of competing orders; particularly, this essential and leading role in ordering the eg orbitals in
effect was attributed to the emerging of nanoscale charge- undoped LaMnO3 (which has the strongest Jahn-Teller
ordered insulating regions at intermediate temperatures, distortion in the family though [18]). It is thus important
which could melt rapidly in the magnetic field [2, 3]. In to quantify the leading mechanisms in the present doped
a slightly more doped system (x = 0.5), all these orders case and uncover the effects of the additional charge de-
coexist [5], providing a unique opportunity for a clean gree of freedom in general.
investigation of the strength and origin of each order. In this Letter, we address the above issues using a
Therefore, the study of half-doped manganites is key to recently developed first-principles Wannier states (WSs)
a proper understanding of the physics of manganites in analysis method [19, 20]. A simple picture emerges to rec-
general and the CMR effect in particular [2, 4]. oncile the traditional Mn3+ /Mn4+ wisdom and observed
Currently, one of the critical questions on “charge- weak CD: The fully occupied orbital-ordered “Mn3+ ”
ordered” half-doped manganites is the recent puzzling WSs are delocalized into the neighboring “Mn4+ ” sites
experimental observation of nearly indiscernible charge and thus CD is significantly reduced. In addition, our
disproportion (CD) [6, 7, 8, 9, 10, 11, 12, 13], in sharp systematic comparison of charges near each atom across
contrast to the long accepted picture of a Mn3+ /Mn4+ a wide doping range indicates that doped holes reside in
checkerboard charge order (CO) with Mn3+ eg orbitals the oxygen atoms. On that basis, we address cautions to
ordered in the CE-type antiferromagnetic background [5]. be taken in the standard atomic Mn3+ /Mn4+ picture in
In search for an alternative interpretation, remarkable ex- such strong charge-transfer systems. Moreover, leading
perimental and theoretical effort has been made to check mechanisms are quantified via derivation of a low-energy
the idea of ‘Zener polarons’ in which all Mn ions are effective Hamiltonian from the WSs analysis. e-e inter-
equivalently charged [9]; however, most of them led to action is found important to the observed charge-orbital
conclusions favoring the traditional Mn3+ /Mn4+ picture orders, by doubling the net energy gain of ordered phase.
[11, 12, 13, 14, 15]. This immediately calls for a quan- Furthermore, physical effects introduced by the charge
titative yet intuitive resolution of weak CD compatible freedom will be discussed in detail. Our findings would
with the Mn3+ /Mn4+ picture. put stringent constraints on the general phase diagram
Another closely related crucial issue is the roles of dif- and microscopic understanding of manganites.
ferent microscopic interactions in the observed orders, in We start with the LDA+U [21, 22] band structure cal-
particular the relevance of electron-electron (e-e) inter- culations of La1/2 Ca1/2 MnO3 , based on the realistic crys-
2

tal structure that consists of 80 atoms in the magnetic is still accumulated within the C-site Mn atomic sphere
unit cell [23]. While LDA substantially underestimates owing to the large tails of the two occupied WSs centered
the band gap [17], inclusion of on-site Hubbard U ( 8eV) at the two neighboring B-sites. Integrating the charges
in LDA+U stabilizes the insulating ground state with a within the atomic spheres around the B- and C-site Mn
band gap of 1.3 eV. The experimentally observed mag- atoms leads to a CD of mere 0.14 e. In this simple pic-
netic and orbital orders as well as weak CD are all well ture, one finds a large difference in the occupation num-
reproduced in the LDA+U ground state [21]. In par- bers of the WSs at the B- and C- sites (∆n = 1), but a
ticular, the Mn sites form a peculiar CE-type long range small difference in real charge. That is, the convenient
magnetic order, i.e., antiferromagnetically coupled zigzag Mn3+ /Mn4+ picture is perfectly applicable and it allows
ferromagnetic (FM) chains in the ab plane. Each of these weak CD, as long as the itinerant nature of manganites
chains consists of alternating Mn bridge- and corner-sites is incorporated via the low-energy WSs rather than the
(abbreviated to B- and C-sites, respectively). As clearly standard “atomic states.”
shown in Fig. 1(a), the most relevant low-energy (near In comparison, to make connection with the conven-
the Fermi level EF ) bands are 16 “eg ” spin-majority tional atomic picture and to better formulate the bro-
bands (corresponding to 8 “spin-up” Mn atoms in our ken symmetry problem with a symmetric starting point,
unit cell) spanning an energy window of 3.2 eV. we construct “atomic-like” WSs (AWSs) of d3z2 −r2 and
Small CD vs. 3+/4+ Picture.—The simplest yet re- dx2 −y2 symmetry centered at each Mn site [Fig. 1(b)],
alistic picture of the CO can be obtained by construct- from the same low-energy (both occupied and unoccu-
ing the energy-resolved WSs from the four fully occu- pied) Hilbert space. In this “atomic” picture, B- and C-
pied bands, each centered at one B-site as illustrated in site AWSs are partially occupied with ∆n = 0.6, which
Fig. 1(a). This occupied B-site eg Wannier orbital of does not appear to reflect the weak CD, either. This pic-
3x2 − r2 or 3y 2 − r2 symmetry (so formal valency is 3+) ture is less convenient for an intuitive and quantitative
contains in its tail the integrated out O 2p orbitals with understanding of the weak CD than the previous one,
considerable weight, indicative of the charge-transfer na- as the latter builds the information of the Hamiltonian
ture of the system. Moreover, this “molecular orbital in and the resulting reduced density matrix into the basis.
the crystal” extends significantly to neighboring C-sites Nevertheless, the weak CD still results within the AWS
on the same zig-zag chain. Therefore, although by con- picture due to the large hybridization with O 2p orbitals
struction the C-site eg WSs (not shown) are completely [Fig. 1(b)], which significantly decreases the charge re-
unoccupied (so formal valency is 4+), appreciable charge siding within the Mn atomic sphere. Clearly, the strong
charge-transfer nature of the system renders it highly in-
appropriate to associate CD with the difference in the
occupation numbers of atomic-like states.
The above consideration is general for charge-transfer
materials. Indeed, as presented in Fig. 2 where the two
end limits of La1−x Cax MnO3 (x = 0, 1) are also con-
sidered, we find that the change in the eg charge within
the Mn atomic sphere is much smaller than in nominal
valency. Moreover, the total eg charge within the Mn
atomic sphere changes only insignificantly upon doping,
contrary to a simple valence picture but consistent with

FIG. 1: (Color online) (a) Left panel: Band structures from


the LDA+U calculations (dots) and Wannier states analy-
sis (lines). Right panel: An occupied Mn3+ B-site Wannier FIG. 2: Based on the LDA+U calculations for
orbital, showing remarkable delocalization. (b) Low-energy La1−x Cax MnO3 (x = 0, 1/2, and 1), the change in Mn
Mn atomic-like Wannier states containing in their tails the eg charge within the Mn atomic sphere is much smaller than
integrated out O 2p orbitals. in nominal valency.
3

experiments [7, 24]. This suggests that it would be in- Now based on the AWSs, CO is measured by ∆n =
teresting to explore the physics of the manganites in the hni∈B i − hnj∈C i = 0.6. It deviates from unit because the
charge-transfer model where the oxygen electronic degree kinetic energy ensures that the ground state is a hybrid of
of freedom is explicitly included [25]. both B- and C-site AWSs, like in the usual tight-binding
Leading Mechanisms.—To identify the leading mech- modeling based on atomic orbitals. However, since the
anisms of the charge-orbital orders in a rigorous for- AWSs considerably extend to neighboring oxygen atoms,
malism, we proceed to derive a realistic effective low- the actual CD is much smaller than ∆n.
energy Hamiltonian, H eff , following our recently devel- With the successful derivation of H eff , the microscopic
oped first-principles WS approach [19]. As clearly shown mechanisms of the charge-orbital orders emerge. First of
in Fig. 1, the low-energy physics concerning charge and all, note that the kinetic term alone is able to produce
orbital orders is mainly the physics of one zig-zag FM the orbital ordered insulating phase [16, 27]: Since the in-
chain, since electron hopping between the antiferromag- tersite interorbital hoppings of the Mn eg electrons along
netically arranged chains is strongly suppressed by the the x and y directions have opposite signs, the occupied
double-exchange effect [16, 26, 27]. Our unbiased first- bonding state is gapped from the unoccupied nonbond-
principles analysis of the 16-band one-particle LDA+U ing and antibonding states (by t and 2t, respectively)
Hamiltonian in the above AWS representation reveals in the enlarged unit cell. As for orbital ordering, the Mn
X γγ ′ † X dy2 −z2 (dx2 −z2 ) orbital on any B-site bridging two C-sites
H eff = − (tij djγ ′ diγ + h.c.) − Ez Tiz along the x (y) direction is irrelevant, as the hopping in-
hijiγγ ′ i tegrals involving it is vanishing. That is, only the d3x2 −r2
X X
+ Ueff ni↑ ni↓ + V ni nj (d3y2 −r2 ) orbital on that B-site is active and the B-sites
i hiji
on the zigzag FM chains have to form an “ordered” pat-
X 1 tern of alternating (3x2 − r2 )/(3y 2 − r2 ) orbitals. How-
− g ( ni Q1i + Tix Q2i + Tiz Q3i ) (1) ever, the kinetic term alone give only ∆n = 0. Clearly,
2 CO is induced by the interactions, Ueff , V , or g.
i
To quantify their relative importance for CO, we calcu-
in addition to the elastic energy K({Qi }). Here d†iγ and late their individual contributions to the total energy gain
diγ are electron creation and annihilation operators at with respect to the aforementioned ∆n = 0 but orbital-
site i with “pseudo-spin” γ defined as | ↑i = |3z 2 − r2 i ordered insulating state in the self-consistent mean-field
and | ↓i = |y 2 − x2 i AWSs, corresponding to pseudo-spin theory. The results are listed in Table I. The first row ob-
operator Tix = (d†i↑ di↓ + d†i↓ di↑ )/2 and Tiz = (d†i↑ di↑ − tained without lattice distortions provides a measure of
d†i↓ di↓ )/2. ni = d†i↑ di↑ + d†i↓ di↓ is the electron occupation the purely electronic mechanisms for CO. Interestingly,
number. The in-plane hoppings are basically symmetry √ although the tendency is weak (−13 meV), e-e interac-
related: t↑↑ ↓↓ ↑↓ ↓↑
ij = t/4, tij = 3t/4, tij = tij = ± 3t/4
tions all together are sufficient to induce a CO, consistent
where the signs depend on hopping along the x or y with the results of our first-principles calculations. The
direction. Ez stands for the oxygen octahedral-tilting second row is obtained for the realistic lattice distortions,
induced crystal field. Ueff and V are effective on-site which shows a dramatic enhancement of CO by the JT
and nearest-neighbor e-e interactions, respectively. g is distortions (−113 meV), given that only half of the Mn
the e-l coupling constant. Qi = (Q1i , Q2i , Q3i ) is the atoms are JT active. Together with a −30 meV gain
octahedral-distortion vector, where Q1i is the breathing from the BM distortion, the e-l interactions overwhelm
mode (BM), and Q2i and Q3i are the Jahn-Teller (JT) the cost of the kinetic (71 meV) and elastic (18 meV) en-
modes [16, 17, 26, 27]. ergy by −57 meV, further stabilizing the observed CO.
The effective Hamiltonian are determined by matching Nevertheless, the −70 meV energy gain from the overall
its self-consistent Hartree-Fock expression with H LDA+U e-e interactions accounts for more than half of the total
[19] owing to the analytical structure of the LDA+U energy gain, illustrating clearly their importance to the
approximation [28]. An excellent mapping results from realization of the resulting ∆n = 0.6. Indeed, a further
t = 0.6 eV, Ez = −0.08 eV, Ueff = 1.65 eV, V = 0.5 eV, analysis reveals that e-l couplings alone (Ueff = V = 0)
and g = 2.35 eV/Å. These numbers are close to those ob- produce ∆n = 0.3, only half of the realistic ∆n, mani-
tained for undoped LaMnO3 [19] (excluding V , which is festing the necessity of including e-e interactions.
inert in the undoped case), and indicates that the spin-
majority eg electrons in the manganites are still in the
intermediate e-e interaction regime with comparable e-l TABLE I: Breakdown of the energy gain (in meV per Mn)
interaction. Furthermore, the rigidity of the low-energy due to the CO formation in the mean-field theory.
parameters upon significant (x = 0.5) doping verifies the
Qi Total Ueff V t BM JT K
validity of using a single set of parameters for a wide 0 -13 -11 -15 12 0 0 0
range of doping levels, a common practice that is not a realistic -127 -22 -48 71 -30 -113 18
priori justified for low-energy effective Hamiltonians.
4

Further insights can be obtained by considering the in- ing only measures a strong ordering of the electron oc-
dividual microscopic roles of these interactions acting to cupation numbers of these Wannier states, while actual
the kinetic-only starting point. First, infinitesimal Ueff or charge disproportion must be substantially reduced. Fur-
g can induce CO, as a result of exploiting the fact that thermore, we have derived a realistic effective low-energy
the B- (C-) site has one (two) active eg orbital: (i) Ueff Hamiltonian, with which the leading mechanisms of the
has no effect on the B-sites; therefore, Ueff pushes the eg observed charge-orbital orders are analyzed. In particu-
electrons to the B-sites, in order to lower the Coulomb lar, we report novel effects of e-e interactions on charge
energy on the C-sites [16]. This is opposite to its nor- ordering in half-doped manganites and demonstrate the
mal behavior of favoring charge homogeneity in systems comparable importance of e-e and e-l interactions.
such as straight FM chains (realized in the C-type anti-
We are grateful to E. Dagotto for stimulating discus-
ferromagnet). (ii) It is favorable to cooperatively induce
sions. Brookhaven National Laboratory is supported by
the (3x2 − r2 )/(3y 2 − r2 )-type JT distortions on the B-
U.S. Department of Energy under Contract No. DE-
sites and the BM distortions on the C-sites in order to
AC02-98CH10886. This work is partially supported by
minimize the elastic energy [5]. These lattice distortions
DOE-CMSN.
lower the relative potential energy of the active orbitals
in the B-sites, also driving the eg electrons there. Hence,
Ueff and e-l interactions work cooperatively in the CO
formation.
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Vc ≃ 0.8 eV to induce CO. This is surprising in compar- Magnetoresistance (Springer-Verlag, Berlin, 2002).
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