The microscopic origin of the magnetically-driven ferroelectricity in collinear AFM-E orthorhombic manganites is explained by means of first-principles Wannier functions. We show that the polarization is mainly determined by the "asymmetric electron hopping" of orbitally-polarized Mn eg states, implicit in the peculiar in-plane zig-zag spin arrangement in the AFM-E configuration. In ortho-HoMnO3, Wannier function centers are largely displaced with respect to corresponding ionic positions, implying that the final polarization is strongly affected by a purely electronic contribution, at variance with standard ferroelectrics where the ionic-displacement is dominant. However, the final value of the polarization is the result of competing effects, as shown by the opposite signs of the contributions to the polarization coming from the Mn eg and t2g states. Furthermore, a systematic analysis of the link between ferroelectricity and the spin, orbital and lattice degrees of freedom in the manganite series has been carried out, in the aim of ascertaining chemical trends as a function of the rare-earth ion. Our results show that the Mn-O-Mn angle is the key quantity in determining the exchange coupling: upon decreasing the Mn-O-Mn angle, the first- (second-) nearest neighbor ferromagnetic (antiferromagnetic) interaction decreases (remains constant), in turn stabilizing either the AFM-A or the AFM-E spin configuration for weakly or strongly distorted manganites, respectively. The Mn eg contribution to the polarization dramatically increases with the Mn-O-Mn angle and decreases with the "long" Mn-O bond length, whereas the Mn t2g contribution decreases with the "short" Mn-O bond-length, partially cancelling the former term.
We argue that the homogeneous distribution of spins in the spin-spiral state of orthorhombic manganites is deformed by the relativistic spin-orbit interaction. The thus induced spin-spiral inhomogeneity gives rise to the ferroelectric response of the purely electronic origin in even-periodic magnetic structures. The mechanism is generic and explains the appearance of ferroelectricity in the twofold periodic structure of HoMnO3 as well as the fourfold periodic structure of TbMnO3. Nevertheless, odd-periodic magnetic structures preserve the inversion symmetry and thus are not ferroelectric. Our …
We show that the symmetry of the spin zigzag chain E phase of the orthorhombic perovskite manganites and nickelates allows for the existence of a finite ferroelectric polarization. The proposed microscopic mechanism is independent of spin-orbit coupling. We predict that the polarization induced by the E-type magnetic order can potentially be enhanced by up to two orders of magnitude with respect to that in the spiral magnetic phases of TbMnO3 and similar multiferroic compounds.
Multiferroic rare earth manganites attracted recent attention because of the coexistence of different types of magnetic and ferroelectric orders resulting in complex phase diagrams and a wealth of physical phenomena. The coupling and mutual interference of the different orders and the large magnetoelectric effect observed in several compounds are of fundamental interest and bear the potential for future applications in which the dielectric (magnetic) properties can be modified by the onset of a magnetic (dielectric) transition or the application of a magnetic (electric) field. The physical mec…
We show that in manganites close to half-doping novel non-bipartite magnetic phases appear due to the interplay between double exchange, superexchange and orbital ordering. In considerable part of the phase diagram the groundstate has a magnetic order that is intermediate between the canonical magnetic CE-phase and a state that we identify as the recently observed Zener polaron state. The intermediate phase shows a type of charge ordering that breaks inversion symmetry and is therefore predicted to be ferroelectric.
We discuss the particle size driven tunability of the coexistence of ferromagnetism and ferroelectricity in Pr0.67Ca0.33MnO3(PCMO) with the help of x ray diffraction, magnetization, impedance spectroscopy, and remanent polarization measurements. The remanent polarization measurements using the positive up negative down method clearly prove the existence of ferroelectricity in PCMO with phase separation between Zener polaron(ZP) ordered P21nm and disordered Pbnm structures. We also find that the ferroelectric response is enhanced in nanocrystalline samples so long as ZP ordering is not destroye…
We demonstrate that small but finite ferroelectric polarization ($\sim$0.01 $μ$C/cm$^2$) emerges in orthorhombic LuFeO$_3$ ($Pnma$) at $T_N$ ($\sim$600 K) because of commensurate (k = 0) and collinear magnetic structure. The synchrotron x-ray and neutron diffraction data suggest that the polarization could originate from enhanced bond covalency together with subtle contribution from lattice. The theoretical calculations indicate enhancement of bond covalency as well as the possibility of structural transition to the polar $Pna2_1$ phase below $T_N$. The $Pna2_1$ phase, in fact, is found to be …
By means of density-functional simulations for half-doped manganites, such as pseudocubic Pr0.5Ca0.5MnO3 and bilayer PrCa2Mn2O7, we discuss the occurrence of ferroelectricity and we explore its crucial relation to the crystal structure and to peculiar charge/spin/orbital ordering effects. In pseudocubic Pr0.5Ca0.5MnO3, ferroelectricity is induced in the Zener polaron type structure, where Mn ions are dimerized. In marked contrast, in bilayer PrCa2Mn2O7, it is the displacements of apical oxygens bonded to either Mn3+ or Mn4+ ions that play a key role in the rising of ferroelectricity. Important…
The single layered manganite Pr$_{0.22}$Sr$_{1.78}$MnO$_4$ undergoes structural transition from high temperature tetragonal phase to low temperature orthorhombic phase below room temperature. The orthorhombic phase was reported to have two structural variants with slightly different lattice parameters and Mn-3$d$ levels show orbital ordering within both the variants, albeit having mutually perpendicular ordering axis. In addition to orbital ordering, the orthorhombic variants also order antiferromagnetically with different Néel temperatures. Our magnetic investigation on the polycrystalline sa…
Aiming at understanding the origin of the electronic contribution to ferroelectric polarization in undoped manganites, we evaluate the Berry phase of orbital-polarizable Bloch electrons as an orbital ordering (OO) establishes in the background of an antiferromagnetic E-type configuration. The onset of OO is tuned by the Jahn-Teller (JT) interaction in a tight-binding model for interacting electrons moving along zigzag chains. A finite polarization is found as soon as the JT coupling is strong enough to induce OO, supporting the large electronic contribution predicted from first principles.
By directly measuring electrical hysteresis loops using the Positive-Up Negative-Down (PUND) method, we accurately determined the remanent ferroelectric polarization Pr of orthorhombic RMnO3 (R = Ho, Tm, Yb, and Lu) compounds below their E-type spin ordering temperatures. We found that LuMnO3 has the largest Pr of 0.17 uC/cm^2 at 6 K in the series, indicating that its single-crystal form can produce a Pr of at least 0.6 \muuC/cm^2 at 0 K. Furthermore, at a fixed temperature, Pr decreases systematically with increasing rare earth ion radius from R = Lu to Ho, exhibiting a strong correlation wit…
We use ab initio electronic structure calculations within the generalized gradient approximation (GGA+U) to density functional theory (DFT) to determine the microscopic exchange interactions in the series of orthorhombic rare-earth manganites, o-$R$MnO$_3$. Our motivation is to construct a model Hamiltonian (excluding effects due to spin-orbit coupling), which can provide an accurate description of the magnetism in these materials. First, we consider TbMnO$_3$, which exhibits a spiral magnetic order at low temperatures. We map the exchange couplings in this compound onto a Heisenberg Hamiltoni…
With the increase of the lattice distortion, the orthorhombic manganites $R$MnO$_3$ ($R$$=$ La, Pr, Nd, Tb, and Ho) are known to undergo the phase transition from the layered A-type antiferromagnetic (AFM) state to the zigzag E-type AFM state. We consider the microscopic origin of this transition. Our approach consists of the two parts. First, we construct an effective lattice fermion model for the manganese 3d-bands and derive parameters of this model from the first-principles electronic structure calculations. Then, we solve this model in the Hartree-Fock approximation (HFA) and analyze the …
We present a rationalization of the Raman spectra of orthorhombic and rhombohedral, stoichiometric and doped, manganese perovskites. In particular we study RMnO3 (R= La, Pr, Nd, Tb, Ho, Er, Y and Ca) and the different phases of Ca or Sr doped RMnO3 compounds as well as cation deficient RMnO3. The spectra of manganites can be understood as combinations of two kinds of spectra corresponding to two structural configurations of MnO6 octahedra and independently of the average structure obtained by diffraction techniques. The main peaks of compounds with regular MnO6 octahedra, as CaMnO3, highly Ca …
In this contribution to the special issue on multiferroics we focus on multiferroicity driven by different forms of charge ordering. We will present the generic mechanisms by which charge ordering can induce ferroelectricity in magnetic systems. There is a number of specific classes of materials for which this is relevant. We will discuss in some detail $(i)$ perovskite manganites of the type (PrCa)MnO$_3$, $(ii)$ the complex and interesting situation in magnetite Fe$_3$O$_4$, $(iii)$ strongly ferroelectric frustrated LuFe$_2$O$_4$, $(iv)$ an example of a quasi one-dimensional organic system. …
Recently we have reported the observation of colossal magnetostriction effect in HoMn2O5 single crystals. Besides we have made the supposition for possible correlation between the peculiarities, observed in the field depended polarization measurements, and the colossal magnetostriction effect at a 4.2 K temperature. In this article we present our results received by polarization and magnetostriction measurements on HoMn2O5 and TbMn2O5 single crystals and the strong correlation between magnetostriction and polarization phase transition for these two compounds. The origin of this correlation is …
We argue that many aspects of improper ferroelectric activity in orthorhombic manganites can be rationalized by considering the limit of infinite intra-atomic splitting between the majority- and minority-spin states (or the double exchange limit), which reduces the problem to the analysis of a spinless double exchange (DE) Hamiltonian. We apply this strategy to the low-energy model, derived from the first-principles calculations, and combine it with the Berry-phase theory of electric polarization. We start with the simplest two-orbital model, describing the behavior of the eg bands, and apply …
Many multiferroic materials, with various chemical compositions and crystal structures, have been discovered in the past years. Among these multiferroics, some perovskite manganites with ferroelectricity driven by magnetic orders are of particular interest. In these multiferroic perovskite manganites, not only their multiferroic properties are quite prominent, but also the involved physical mechanisms are very plenty and representative. In this Brief Review, we will introduce some recent theoretical and experimental progress on multiferroic manganites.
We have investigated dielectric properties in Mott insulators GdMnO$_{3}$ and TbMnO$_{3}$ under magnetic fields and external quasihydrostatic pressures. In the case of GdMnO$_{3}$, thermal hysteresis for dielectric constant $ε$ and discontinuous lattice distortion were observed at ferroelectric transition temperature ($T_{C}$), and ferroelectric spontaneous polarization was suppressed by application of external pressure. These results indicate that the ferroelectric transition in GdMnO$_{3}$ is a first-order displacive-type one. On the other hand, the thermal hysteresis and discontinuous latti…
The experimental observation of multiferroic behavior in perovskite manganites with a spiral spin structure demands to clarify the origin of these magnetic states and their relation to ferroelectricity. We show that spin-spiral phases with diagonal wavevector and also the E-type phase exist for intermediate values of the Hund's rule and the Jahn-Teller coupling in the orbitally ordered and insulating state of the standard two-band model Hamiltonian for manganites. Our results support the spin-current mechanism for ferroelectricity and present an alternative view to earlier conclusions where fr…
We have investigated dielectric properties in a series of crystals of $R$MnO$_{3}$ ($R$ is a rare earth ion) under magnetic fields and quasihydrostatic pressure. We have found that ferroelectric phase appeared in GdMnO$_3$ crystal below 13K. We have confirmed that a small spontaneous polarization exists along a axis ($P_a$) in the orthorhombic $Pbnm$ setting and that $P_a$ can be reversed by the dc electric field. The dielectric anomaly due to the ferroelectric transition accompanied thermal hysteresis and lattice striction. The ferroelectric transition temperature decreased with quasihydrosta…
We have investigated orthorhombic $R$MnO$_{3}$ ($R$=(Gd$_{1-y}$Tb$_{y}$)) crystals near the phase boundary between the paraelectric $A$-type-antiferromagnetic (AF) phase (PA) and the ferroelectric transverse-spiral-AF one (FS). The spiral AF structure breaks inversion symmetry and induces the ferroelectric polarization through the inverse Dzyaloshinskii-Moriya (DM) interaction. We have found that the PA-FS phase boundary is located at around 0.15$<$$y$$<$0.2. In $y$=0.15 compound, PA and FS phases appear in cooling scan, while FS is not observed in warming scan. This result suggests that FS ob…
We show that the transition in AMnO3 from the orthorhombic perovskite phase to the hexagonal phase is promoted by inducing disorder on the A-site. The gap between the orthorhombic and the hexagonal phase is widened for disordered, mixed yttrium-gadolinium manganite samples. At the cost of the orthorhombic phase a two phase region emerges. The phase separation exhibits very unusual thermodynamical behaviour. We also show that high pressure synthesis favours the orthorhombic phase. YMnO3 is formed in the orthorhombic phase at 15 kbar.
Ferroelectricity is observed in orthorhombic $HoMnO_3$ and $YMnO_3$ at the magnetic lock-in transitions into an E-type structure or an incommensurate phase with a temperature independent wave vector, respectively. In $HoMnO_3$ the ferroelectric polarization strongly depends on the external magnetic field indicating the involvement of the rare earth moment order in this compound. The results are discussed within the framework of recent theoretical models, in particular the double exchange driven polar displacements predicted for E-type magnetic structures.
This work reports an experimental investigation of the magneto-elastic coupling and polarization character of magnetic phases of the orthorhombic Eu1-xYxMnO3 system at low temperatures. The temperature dependence of the polarization reversal curves clearly reveals the existence of a reentrant improper ferroelectric phase for x = 0.2 and 0.3. Although a ferroelectric phase is also stable for x = 0.4, we have no experimental evidence that it vanishing at finite temperatures. From these results and those obtained from other experimental techniques, the corresponding (x,T) phase diagram was traced…
Using first principles calculations, we study the microscopic origin of ferroelectricity (FE) induced by magnetic order in the orthorhombic HoMnO3. We obtain the largest ferroelectric polarization observed in the whole class of improper magnetic ferroelectrics to date. We find that the two proposed mechanisms for FE in multiferroics, lattice- and electronic-based, are simultaneously active in this compound: a large portion of the ferroelectric polarization arises due to quantum-mechanical effects of electron orbital polarization, in addition to the conventional polar atomic displacements. An i…
Orthorhombically distorted perovskite manganites, RMnO3 with R being a trivalent rare-earth ion, exhibit a variety of magnetic and electric phases including multiferroic (i.e. concurrently magnetic and ferroelectric) phases and fascinating magnetoelectric phenomena. We theoretically study the phase diagram of RMnO3 by constructing a microscopic spin model, which includes not only the superexchange interaction but also the single-ion anisotropy (SIA) and the Dzyaloshinsky-Moriya interaction (DMI). Analysis of this model using the Monte-Carlo method reproduces the experimental phase diagrams as …
Improper ferroelectricity (trimerization) in the hexagonal manganites RMnO$_3$ leads to a network of coupled structural and magnetic vortices that induce domain wall magnetoelectricity and magnetization neither of which, however, occurs in the bulk. Here we combined first-principles calculations, group-theoretic techniques, and microscopic spin models to show how the trimerization not only induces a polarization but also a bulk magnetization and bulk magnetoelectric (ME) effect. This results in the existence of a bulk linear ME vortex structure or a bulk ME coupling such that if direction of p…
The double exchange (DE) model is systematically applied for studying the coupling between ferroelectric (FE) and magnetic orders in several prototypical types of multiferroic manganites. The model was constructed for the magnetically active Mn $3d$ bands in the basis of Wannier functions and include the effect of screened on-site Coulomb interactions. The essence of our approach for the FE polarization is to use the Berry phase theory, formulated in terms of occupied Wannier functions, and to evaluate the asymmetric spin-dependent change of these functions in the framework of the DE model. Th…
In magnetic compounds with Jahn-Teller (JT) ions (such as Mn3+ or Cu2+), the ordering of the electron or hole orbitals is associated with cooperative lattice distortions. There the role of JT effect, although widely recognised, is still elusive in the ground state properties. We suggest that, in these materials, there exist elementary excitations whose energy spectrum is described in terms of the total angular momentum eigenstates and is quantised as in quantum rotors found in JT centers. We observed features originating from these excitations in the optical spectra of a model compound LaMnO3 …
TbMnO3 is an orthorhombic insulator where incommensurate spin order for temperature T_N < 41K is accompanied by ferroelectric order for T < 28K. To understand this, we establish the magnetic structure above and below the ferroelectric transition using neutron diffraction. In the paraelectric phase, the spin structure is incommensurate and longitudinally-modulated. In the ferroelectric phase, however, there is a transverse incommensurate spiral. We show that the spiral breaks spatial inversion symmetry and can account for magnetoelectricity in TbMnO3.
There has been tremendous research activity in the field of magneto-electric (ME) multiferroics after Kimura et al. [1] showed that antiferromagnetic and ferroelectric order coexist in orthorhom- bically distorted perovskite TbMnO3 and are strongly coupled. It is now generally accepted that ferroelectricity in TbMnO3 is induced by magnetic long range order that breaks the symmetry of the crystal and creates a polar axis [2]. One remaining key question is whether magnetic order can induce ferroelectric polarization that is as large as that of technologically useful materials. We show that ferro…
First-principles calculations have been performed for different collinear magnetic orderings in orthorhombic manganites, such as HoMnO3, TbMnO3 and YMnO3, showing large GdFeO3-like distortions. Our results suggest that the AFM-E type ordering, experimentally observed in HoMnO3 and recently proposed from model hamiltonian studies as a potentially novel phase, is indeed the magnetic ground state. Its stability is strongly connected with octahedral distortions and points to the relevance of structural more than chemical effects. The calculated exchange constants, extracted from a Heisenberg model…
We have studied the effects of band filling and bandwidth control on the chemical potential in perovskite manganites $R_{1-x}A_x$MnO$_3$ ($R$ : rare earth, $A$ : alkaline earth) by measurements of core-level photoemission spectra. A suppression of the doping-dependent chemical potential shift was observed in and around the CE-type charge-ordered composition range, indicating that there is charge self-organization such as stripe formation or its fluctuations. As a function of bandwidth, we observed a downward chemical potential shift with increasing bandwidth due to the reduction of the orthorh…
We analyze the symmetry changes of the paramagnetic to the A-type antiferromagnetic and to the ferromagnetic phase transitions in undoped and moderately doped LaMnO$_3$, respectively. We show that in the orthorhombic-distorted perovskite manganites the phase separation at low doping is associated with the noncollinear nature of the magnetic orders permitted by symmetry. A simple model for the competition between the two phase transitions is put forward within the framework of Landau theory of phase transitions.
We have investigated the magnetic and dielectric properties of orthorhombic Eu$_{1-y}$Y$_y$MnO$_3$ ($0\leq y\leq 0.6$) single crystals without the presence of the 4$f$ magnetic moments of the rare-earth ions. In $y\geq 0.2$, the magnetic-structure driven ferroelectricity is observed. The ferroelectric transition temperature is steeply reducing with increasing $y$. In $y\geq 0.52$, two ferroelectric phases ($P\parallel a$ and $P\parallel c$) are coexistent at low temperatures. In these phases, ferroelectricity has different origin, which is evidenced by the distinctive poling-electric-field dep…
We investigate spin-charge-orbital ordering in a Mn$^{3+}$/Mn$^{4+}$ mixed valence state on a hollandite-type lattice using unrestricted Hartree-Fock calculation on a multi-band Mn 3$d$-O 2$p$ lattice model. The calculations show that the Mn$^{3+}$-Mn$^{4+}$ double exchange interaction, the Mn$^{3+}$-Mn$^{3+}$ and Mn$^{4+}$-Mn$^{4+}$ superexchange interactions are ferromagnetic and play important roles to stabilize the charge and orbital ordering pattern. The most stable charge and orbital ordering pattern is consistent with the $1\times1\times1$ orthorhombic or monoclinic structure of K$_{1.6…
We report a pervasive phenomenon of gradual emergence of negative magnetization in typical $R_{1-x}D_x$MnO$_3$ orthorhombic perovskite manganites in nano form (with $R^{3+}$ being a trivalent high-magnetic-moment ion from the heavier rare-earth elements Gd, Tb, Dy and $D^{2+}$ refers to divalent alkaline elements Sr, Ca, etc.), while the bulk form manifests no negative magnetization. Extensive magnetization studies have been carried out in Gd$_{1-x}$Ca$_x$MnO$_3$ manganites around half doping. We demonstrate experimentally that particle size reduction in nano-form manganites enhances the prope…
We studied the correlation between magnetic, electrical, structural, and magnetostriction properties of the electron doped manganites Ca$_x$Sm$_{1-x}$MnO$_3$ (x = 0.85, 0.8). The paramagnetic to antiferromagnetic transition in both the compounds while cooling is accompanied by an abrupt increase of the spontaneous volume thermal expansion ($Δ$V/V = 0.07 % for x = 0.85 and 0.25 % for x = 0.2). The x = 0.15 exhibits multiple phase separation at 5 K: G-type, and C-type antiferromagnetic phases in orthorhombic (\QTR{it}{Pnma}) and monoclinic (\QTR{it}{P2}$_1$\QTR{it}{/m}) structures respectively. …
The effect of Pr-doping on structural, magnetic and transport properties in electron-doped manganites La0.9-xPrxTe0.1MnO3 with fixed carrier concentration are investigated. The room temperature structural transition from rhombohedral (R3C) to orthorhombic (Pbnm) symmetry is found in the samples with by the Rietveld refinement of x-ray powder diffraction patterns. The Curie temperature of samples decreases and the transition becomes broader with increasing Pr-doping level. For the samples with, there exist insulator-metal (I-M) transition. And the low-temperature I-M transition is observed at a…
Recent progress in the field of multiferroics led to the discovery of many new materials in which ferroelectricity is induced by cycloidal spiral orders. The direction of the electric polarization is typically constrained by spin anisotropies and magnetic field. Here, we report that the mixed rare-earth manganite, Gd$_{0.5}$Dy$_{0.5}$MnO$_3$, exhibits a spontaneous electric polarization along a general direction in the crystallographic ac-plane, which is suppressed below 10 K but re-emerges in an applied magnetic field. Neutron diffraction measurements show that the polarization direction resu…
We present a systematic study of the structure and lattice dynamics at room temperature, and the phonon behavior at low temperatures in orthorhombic Gd$_{1-x}$Y$_{x}$MnO$_{3}$ manganites, with 0 $\leq$ x $\leq$ 0.4, using powder x-ray diffraction and Raman scattering. A thorough analysis towards the correlation between both structural and Raman modes parameters was undertaken. The data obtained at room temperature reveal structural distortions arising from the Jahn-Teller distortion and octahedra tilting. The Jahn-Teller distortion is apparently x-independent, while an increase of Mn-O1-Mn bon…
Using {\it ab initio} density functional theory and single-orbital Hubbard model calculations via the density matrix renormalization group method, we systematically studied the monolayer VOI$_2$ with a $3d^1$ electronic configuration. Our phonon calculations indicate that the orthorhombic $Pmm2$ FE-II phase is the most likely ground state, involving a ferroelectric distortion along the $a$-axis and V-V dimerization along the $b$-axis. Specifically, the "pseudo Jahn-Teller" effect caused by the coupling between empty V ($d_{xz/yz}$ and $d_{3z^2-r^2}$) and O $2p$ states is proposed as the mechan…
We summarize the existing experimental data on electromagnons in multiferroic RMn2O5 compounds, where R denotes a rare earth ion, Y or Bi, and discuss a realistic microscopic model of these materials based on assumption that the microscopic mechanism of magnetically-induced ferroelectricity and electromagnon absorption relies entirely on the isotropic Heisenberg exchange and magnetostrictive coupling of spins to a polar lattice mode and does not involve relativistic effects. This model explains many magnetic and optical properties of RMn2O5 manganites, such as the spin re-orientation transitio…
A series of manganites Tb1-xHoxMnO3 (0<=x<=0.6) with orthorhombic structure are synthesized and detailed investigations on their multiferroicity are performed. Successive magnetic transitions upon temperature variation are evidenced for all samples, and both the Mn3+ spiral spin ordering and rare-earth spin ordering are suppressed with increasing x. Significant enhancement of both the polarization and magnetoelectric response within 0.2<x<0.4 is observed, which may be ascribed to the competition possibly existing between spiral and E-type spin orders. Theoretical calculation is given based on …
We use neutron scattering to study the lattice and magnetic structure of the layered half-doped manganite Pr$_{0.5}$Ca$_{1.5}$MnO$_4$. On cooling from high temperature, the system first becomes charge- and orbital- ordered (CO/OO) near $T_{CO}=300$ K and then develops checkerboard-like antiferromagnetic (AF) order below $T_{N}=130$ K. At temperatures above $T_{N}$ but below $T_{CO}$ ($T_N<T<T_{CO}$), the appearance of short-range AF spin correlations suppresses the CO/OO induced orthorhombic strain, contrasting with other half-doped manganites, where AF order has no observable effect on the la…
Our detailed temperature dependent synchrotron powder x-ray diffraction studies along with first-principles density functional perturbation theory calculations, enable us to shed light on the origin of ferroelectricity in GdCrO3. The actual lattice symmetry is found to be noncentrosymmetric orthorhombic Pna21 structure, sup- porting polar nature of the system. Polar distortion is driven by local symmetry breaking and by local distortions dominated by Gd off-centering. Our study reveals an intimate analogy between GdCrO3 and YCrO3. However, a distinctive difference exists that Gd is less displa…
