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By means of single-crystal X-ray diffraction we have revealed the breaking of centrosymmetry when lowering the temperature under T$_s$ = 200 K concomitantly with the setting of a commensurate superstructure in the small A-site quadruple perovskite YMn$_3$Mn$_4$O$_{12}$. This results is in agreement with all data already reported for this compounds and solve the previous inconsistency about the Yttrium position. The superstructure is characterized by the appearing of satellite reflections in the single crystal pattern, consistent with an I-centered pseudo-orthorhombic commensurate supercell with $a \approx \sqrt{a_F} = 10.4352(7)$ \AA, $b \approx 2b_F = 14.6049(9)$ \AA, $c \approx \sqrt{c_F} = 10.6961(7)$ \AA and $\beta = 90.110(3)^\circ$, where F stands for the "fundamental" high-temperature cell ($a_F \approx c_F \approx 7.45$ \AA, $b_F \approx 7.34$ \AA, and $\beta \approx 90^\circ$). The space-group was unequivocally found to be Ia, which is non polar, thus allowing for a non-zero polarization in the material. We then have investigated in detail the pyrocurrent, transport, dielectric and the DC and AC magnetic properties of polycrystalline sample of YMn$_3$Mn$_4$O$_{12}$ over a wide temperature range. These measurements clearly highlight several critical temperatures in the material and correlation between the different orders: i) the centrosymmetry is broken at high temperature (T$_S$ = 200K), ii) then the long-range magnetic order of B-sites occurs at T$_{N,B}$ = 108 K and at this same temperature the compound enters in an insulating dielectric state. iii) Finally, a remnant polarization is stabilized concomitantly with a magnetic anomaly at T* = 70 K. We propose that YMn$_3$Mn$_4$O$_{12}$ is a peculiar magnetic ferroelectric in which the polar state is driven by short-range magnetic order.

By means of in situ synchrotron X-ray diffraction and Raman spectroscopy under hydrostatic pressure, we investigate the structural stability of the quadruple perovskite LaMn7O12. At 34 GPa, the data unveil a first-order structural phase transition from monoclinic I2/m to cubic Im-3 symmetry characterized by a pronounced contraction of the unit cell and by a significant modifications in the Raman phonon modes. The phase transition is also marked by the suppression of Jahn-Teller distortion which is present in the ambient monoclinic phase. In addition, above 20 GPa pressure, a sudden and simultaneous broadening is observed in several Raman modes which suggests the onset of a sizable electron-phonon interaction and incipient charge mobility. Considering that LaMn7O12 is paramagnetic insulator at ambient, and Jahn-Teller distortion is frozen in the high-pressure Im-3 phase, we argue that this phase could be a potential candidate to host a purely electronic insulator-metal transition with no participation of the lattice, Comment: 6 pages, 4 figures

Pyroelectric current and magnetoelectric coupling measurements on polycrystalline samples of the quadruple perovskite (LaMn$_{3}$)Mn$_{4}$O$_{12}$ give evidence of ferroelectricity driven by the antiferromagnetic ordering of the $B$-site Mn$^{3+}$ ions at $T_{N,B}$=78 K with record values of remnant electric polarization up to $P$=0.56 $\mu$C cm$^{-2}$. X-ray diffraction measurements indicates an anomalous behavior of the monoclinic $\beta$ angle at $T_{N,B}$, which suggests that $P$ lies in the $ac$-plane, where the moments are collinear, so we conclude that exchange striction is the mechanism of spin-driven ferroelectricity. Polarization values $\sim$3 $\mu$C cm$^{-2}$ are expected in single crystals, which would open the avenue towards practical multiferroic applications., Comment: 5 pages, 5 figures

We present the discovery and refinement by neutron powder diffraction of a new magnetic phase in the Na1-xCaxMn7O12 quadruple perovskite phase diagram, which is the incommensurate analogue of the well-known pseudo-CE phase of the simple perovskite manganites. We demonstrate that incommensurate magnetic order arises in quadruple perovskites due to the exchange interactions between A and B sites. Furthermore, by constructing a simple mean field Heisenberg exchange model that generically describes both simple and quadruple perovskite systems, we show that this new magnetic phase unifies a picture of the interplay between charge, magnetic and orbital ordering across a wide range of compounds., Comment: Accepted for publication in Physical Review Letters

BiMnO3 (BMO), ferromagnetic (FM) below Tc = 100 K, was believed to be also ferroelectric (FE) due to a non-centro-symmetric C2 structure, until diffraction data indicated that its space group is the centro-symmetric C2/c. Here we present infrared phonon spectra of BMO, taken on a mosaic of single crystals, which are consistent with C2/c at any T > 10 K, as well as room-temperature Raman data which strongly support this conclusion. We also find that the infrared intensity of several phonons increases steadily for decreasing T, causing the relative permittivity of BMO to vary from 18.5 at 300 K to 45 at 10 K. At variance with FE materials of displacive type, no appreciable softening has been found in the infrared phonons. Both their frequencies and intensities, moreover, appear insensitive to the FM transition at Tc.

The goal of this work is studying the evolution of thermoelectric transport across the members of the Ruddlesden-Popper series iridates Srn+1IrnO3n+1, where a metal-insulator transition driven by bandwidth change occurs, from the strongly insulating Sr2IrO4 to the metallic non Fermi liquid behavior of SrIrO3. Sr2IrO4 (n=1), Sr3Ir2O7 (n=2) and SrIrO3 (n=inf.) polycrystals are synthesized at high pressure and characterized by structural, magnetic, electric and thermoelectric transport analyses. We find a complex thermoelectric phenomenology in the three compounds. Thermal diffusion of charge carriers accounts for the Seebeck behavior of Sr2IrO4, whereas additional drag mechanisms come into play in determining the Seebeck temperature dependence of Sr3Ir2O7 and SrIrO3. These findings reveal close relationship between magnetic, electronic and thermoelectric properties, strong coupling of charge carriers with phonons and spin fluctuations as well as relevance of multiband description in these compounds., Comment: main paper + supplementary information

By means of synchrotron x-ray and electron diffraction, we studied the structural changes at the charge order transition $T_{CO}$=176 K in the mixed-valence quadruple perovskite (NaMn$_3$)Mn$_4$O$_{12}$. Below $T_{CO}$ we find satellite peaks indicating a commensurate structural modulation with the same propagation vector q =(1/2,0,-1/2) of the CE magnetic order that appears at low temperature, similarly to the case of simple perovskites like La$_{0.5}$Ca$_{0.5}$MnO$_3$. In the present case, the modulated structure together with the observation of a large entropy change at $T_{CO}$ gives evidence of a rare case of full Mn$^{3+}$/Mn$^{4+}$ charge and orbital order consistent with the Goodenough-Kanamori model., Comment: Accepted for publication in Phys. Rev. B Rapid Communications

We report on a systematic study of the structural, magnetic and transport properties of high-purity 1T-VS$_2$ powder samples prepared under high pressure. The results differ notably from those previously obtained by de-intercalating Li from LiVS$_2$. First, no Charge Density Wave (CDW) is found by transmission electron microscopy down to 94 K. Though, \textit{ab initio} phonon calculations unveil a latent CDW instability driven by an acoustic phonon softening at the wave vector ${\bf q}_{CDW} \approx$ (0.21,0.21,0) previously reported in de-intercalated samples. A further indication of latent lattice instability is given by an anomalous expansion of the V-S bond distance at low temperature. Second, infrared optical absorption and electrical resistivity measurements give evidence of non metallic properties, consistent with the observation of no CDW phase. On the other hand, magnetic susceptibility and NMR data suggest the coexistence of localized moments with metallic carriers, in agreement with \textit{ab initio} band structure calculations. This discrepancy is reconciled by a picture of electron localization induced by disorder or electronic correlations leading to a phase separation of metallic and non-metallic domains in the nm scale. We conclude that 1T-VS$_2$ is at the verge of a CDW transition and suggest that residual electronic doping in Li de-intercalated samples stabilizes a uniform CDW phase with metallic properties., Comment: 22 pages, 10 Figures. Full resolution pictures available at http://journals.aps.org/prb/abstract/10.1103/PhysRevB.89.235125

We suggest, and demonstrate, a systematic approach to the study of cuprate superconductors, namely, progressive change of ion size in order to systematically alter the interaction strength and other key parameters. R(Ba,Sr)$_2$Cu$_3$O$_y$ (R={La, ... Lu,Y}) is such a system where potentially obscuring structural changes are minimal. We thereby systematically alter both dielectric and magnetic properties. Dielectric fluctuation is characterized by ionic polarizability while magnetic fluctuation is characterized by exchange interactions measurable by Raman scattering. The range of transition temperatures is 70 to 107 K and we find that these correlate only with the dielectric properties, a behavior which persists with external pressure. The ultimate significance may remain to be proven but it highlights the role of dielectric screening in the cuprates and adds support to a previously proposed novel pairing mechanism involving exchange of quantized waves of electronic polarization., Comment: Manuscript: 5 pages, 4 figures. Supplemental material included (9 pages, 5 figures)

A quarter of a century after their discovery the mechanism that pairs carriers in the cuprate high-Tc superconductors (HTS) still remains uncertain. Despite this the general consensus is that it is probably magnetic in origin [1] so that the energy scale for the pairing boson is governed by J, the antiferromagnetic exchange interaction. Recent studies using resonant inelastic X-ray scattering strongly support these ideas [2]. Here as a further test we vary J (as measured by two-magnon Raman scattering) by more than 60% by changing ion sizes in the model HTS system LnA2Cu3O7-{\delta} where A=(Ba,Sr) and Ln=(La, Nd, Sm, Eu, Gd, Dy, Yb, Lu). Such changes are often referred to as "internal" pressure. Surprisingly, we find Tcmax anticorrelates with J where internal pressure is the implicit variable. This is the opposite to the effect of external pressure and suggests that J is not the dominant energy scale governing Tcmax., Comment: 8 pages, 3 figures

By means of neutron powder diffraction, we investigated the effect of the polar Bi$^{3+}$ ion on the magnetic ordering of the Mn$^{3+}$ ions in BiMn$_3$Mn$_4$O$_{12}$, the counterpart with \textit{quadruple} perovskite structure of the \textit{simple} perovskite BiMnO$_3$. The data are consistent with a \textit{noncentrosymmetric} spacegroup $Im$ which contrasts the \textit{centrosymmetric} one $I2/m$ previously reported for the isovalent and isomorphic compound LaMn$_3$Mn$_4$O$_{12}$, which gives evidence of a Bi$^{3+}$-induced polarization of the lattice. At low temperature, the two Mn$^{3+}$ sublattices of the $A'$ and $B$ sites order antiferromagnetically (AFM) in an independent manner at 25 and 55 K, similarly to the case of LaMn$_3$Mn$_4$O$_{12}$. However, both magnetic structures of BiMn$_3$Mn$_4$O$_{12}$ radically differ from those of LaMn$_3$Mn$_4$O$_{12}$. In BiMn$_3$Mn$_4$O$_{12}$ the moments $\textbf{M}_{A'}$ of the $A'$ sites form an anti-body AFM structure, whilst the moments \textbf{M}$_{B}$ of the $B$ sites result from a large and \textit{uniform} modulation $\pm \textbf{M}_{B,b}$ along the b-axis of the moments \textbf{M}$_{B,ac}$ in the $ac$-plane. The modulation is strikingly correlated with the displacements of the Mn$^{3+}$ ions induced by the Bi$^{3+}$ ions. Our analysis unveils a strong magnetoelastic coupling between the internal strain created by the Bi$^{3+}$ ions and the moment of the Mn$^{3+}$ ions in the $B$ sites. This is ascribed to the high symmetry of the oxygen sites and to the absence of oxygen defects, two characteristics of quadruple perovskites not found in simple ones, which prevent the release of the Bi$^{3+}$-induced strain through distortions or disorder. This demonstrates the possibility of a large magnetoelectric coupling in proper ferroelectrics and suggests a novel concept of internal strain engineering for multiferroics design., Comment: 9 pages, 7 figures, 5 tables

A first order structural Jahn-Teller transition at T_{JT} = 650 K has been recently reported for the quadruple perovskite LaMn7O12 . We have carried out magnetization and transport measurements below and above T_{JT} in order to investigate the effect of the transition. Electrical conduction turns out to be polaronic, changing from non-adiabatic to adiabatic through the transition. Magnetic behavior can be described by non-interacting Mn3+ ions below T_{JT}, while above T_{JT} it is of questionable interpretation. The effect of thermal cycling on as grown samples of different purity degree also allowed us to clarify the intrinsic magnetic response of LaMn7O12 at lower temperatures., Comment: 5 pages, 4 figures

We report on the high pressure synthesis of BiMn$_7$O$_{12}$, a manganite displaying a "quadruple perovskite" structure. Structural characterization of single crystal samples shows a distorted and asymmetrical coordination around the Bi atom, due to presence of the $6s^{2}$ lone pair, resulting in non-centrosymmetric space group Im, leading to a permanent electrical dipole moment and ferroelectric properties. On the other hand, magnetic characterization reveals antiferromagnetic transitions, in agreement with the isostructural compounds, thus evidencing two intrinsic properties that make BiMn$_7$O$_{12}$ a promising multiferroic material., Comment: 4 pages, 3 figures

The structural properties of BiMn$O_3$ were determined from neutron powder diffraction data as a function of temperature and magnetic field. The structure at all temperatures was found to be centrosymmetric with space group $C2/c$, which is incompatible with ferroelectricity. At T$_C\simeq 100 K$, we observed the onset of a large magnetoelastic strain, proportional to the square of the magnetization. We interpret this structural rearrangement, together with the previously observed magnetodielectric anomalies, as due to the need to optimize the partially frustrated magnetic interactions., Comment: 4 pages, 4 figures