Stabilization of the high-spin state of Co3+^{3+} in LaCo1−x_{1-x}Rhx_{x}O3_3

The rhodium doping in the LaCo$_{1-x}$Rh$_{x}$O$_3$ perovskite series ($x=0.02-0.5$) has been studied by X-ray diffraction, electric transport and magnetization measurements, complemented by electronic structure GGA+U calculations in supercell for different concentration regimes. No charge transfer between Co$^{3+}$ and Rh$^{3+}$ is evidenced. The diamagnetic ground state of LaCoO$_3$, based on Co$^{3+}$ in low-spin (LS) state, is disturbed even by a small doping of Rh. The driving force is the elastic energy connected with incorporation of a large Rh$^{3+}$ cation into the matrix of small LS Co$^{3+}$ cations, which is relaxed by formation of large Co$^{3+}$ in high-spin (HS) state in the next-nearest sites to the inserted Rh atom. With increasing temperature, the population of Co$^{3+}$ in HS state increases through thermal excitation, and a saturated phase is obtained close to room temperature, consisting of a nearest-neighbor correlation of small (LS Co$^{3+}$) and large (HS Co$^{3+}$ and LS Rh$^{3+}$) cations in a kind of double perovskite structure. The stabilizing role of elastic and electronic energy contributions is demonstrated in supercell calculations for dilute Rh concentration compared to other dopants with various trivalent ionic radius.Comment: 8 pages, 8 figure

Metal-insulator transition and the Pr3+^{3+}/Pr4+^{4+} valence shift in (Pr1−y_{1-y}Yy_{y})0.7_{0.7}Ca0.3_{0.3}CoO3_3

The magnetic, electric and thermal properties of the ($Ln_{1-y}$Y$_{y}$)$_{0.7}$Ca$_{0.3}$CoO$_3$ perovskites ($Ln$~=~Pr, Nd) were investigated down to very low temperatures. The main attention was given to a peculiar metal-insulator transition, which is observed in the praseodymium based samples with $y=0.075$ and 0.15 at $T_{M-I}=64$ and 132~K, respectively. The study suggests that the transition, reported originally in Pr$_{0.5}$Ca$_{0.5}$CoO$_3$, is not due to a mere change of cobalt ions from the intermediate- to the low-spin states, but is associated also with a significant electron transfer between Pr$^{3+}$ and Co$^{3+}$/Co$^{4+}$ sites, so that the praseodymium ions occur below $T_{M-I}$ in a mixed Pr$^{3+}$/Pr$^{4+}$ valence. The presence of Pr$^{4+}$ ions in the insulating phase of the yttrium doped samples (Pr$_{1-y}$Y$_{y}$)$_{0.7}$Ca$_{0.3}$CoO$_3$ is evidenced by Schottky peak originating in Zeeman splitting of the ground state Kramers doublet. The peak is absent in pure Pr$_{0.7}$Ca$_{0.3}$CoO$_3$ in which metallic phase, based solely on non-Kramers Pr$^{3+}$ ions, is retained down to the lowest temperature.Comment: 10 figure

Magnetodielectric effect and optic soft mode behaviour in quantum paraelectric EuTiO3 ceramics

Infrared reflectivity and time-domain terahertz transmission spectra of EuTiO3 ceramics revealed a polar optic phonon at 6 - 300K, whose softening is fully responsible for the recently observed quantum paraelectric behaviour. Even if our EuTiO3 ceramics show lower permittivity than the single crystal due to a reduced density and/or small amount of secondary pyrochlore Eu2Ti2O7 phase, we confirmed the magnetic field dependence of the permittivity, also slightly smaller than in single crystal. Attempt to reveal the soft phonon dependence at 1.8K on the magnetic field up to 13T remained below the accuracy of our infrared reflectivity experiment

Synchronization of multi-phase oscillators: An Axelrod-inspired model

Inspired by Axelrod's model of culture dissemination, we introduce and analyze a model for a population of coupled oscillators where different levels of synchronization can be assimilated to different degrees of cultural organization. The state of each oscillator is represented by a set of phases, and the interaction --which occurs between homologous phases-- is weighted by a decreasing function of the distance between individual states. Both ordered arrays and random networks are considered. We find that the transition between synchronization and incoherent behaviour is mediated by a clustering regime with rich organizational structure, where some of the phases of a given oscillator can be synchronized to a certain cluster, while its other phases are synchronized to different clusters.Comment: 6 pages, 5 figure

Hole-doping dependence of percolative phase separation in Pr_(0.5-delta)Ca_(0.2+delta)Sr_(0.3)MnO_(3) around half doping

We address the problem of the percolative phase separation in polycrystalline samples of Pr$_{0.5-\delta}$Ca$_{0.2+\delta}$Sr$_{0.3}$MnO$_3$ for $-0.04\leq \delta \leq 0.04$ (hole doping $n$ between 0.46 and 0.54). We perform measurements of X-ray diffraction, dc magnetization, ESR, and electrical resistivity. These samples show at $T_C$ a paramagnetic (PM) to ferromagnetic (FM) transition, however, we found that for $n>0.50$ there is a coexistence of both of these phases below $T_C$. On lowering $T$ below the charge-ordering (CO) temperature $T_{CO}$ all the samples exhibit a coexistence between the FM metallic and CO (antiferromagnetic) phases. In the whole $T$ range the FM phase fraction ($X$) decreases with increasing $n$. Furthermore, we show that only for $n\leq 0.50$ the metallic fraction is above the critical percolation threshold $X_C\simeq 15.5$. As a consequence, these samples show very different magnetoresistance properties. In addition, for $n\leq 0.50$ we observe a percolative metal-insulator transition at $T_{MI}$, and for $T_{MI}<T<T_{CO}$ the insulating-like behavior generated by the enlargement of $X$ with increasing $T$ is well described by the percolation law $\rho ^{-1}=\sigma \sim (X-X_C)^t$, where $t$ is a critical exponent. On the basis of the values obtained for this exponent we discuss different possible percolation mechanisms, and suggest that a more deep understanding of geometric and dimensionality effects is needed in phase separated manganites. We present a complete $T$ vs $n$ phase diagram showing the magnetic and electric properties of the studied compound around half doping.Comment: 9 text pages + 12 figures, submitted to Phys. Rev.

First-principles design and subsequent synthesis of a material to search for the permanent electric dipole moment of the electron

We describe the first-principles design and subsequent synthesis of a new material with the specific functionalities required for a solid-state-based search for the permanent electric dipole moment of the electron. We show computationally that perovskite-structure europium barium titanate should exhibit the required large and pressure-dependent ferroelectric polarization, local magnetic moments, and absence of magnetic ordering even at liquid helium temperature. Subsequent synthesis and characterization of Eu$_{0.5}$Ba$_{0.5}$TiO$_3$ ceramics confirm the predicted desirable properties.Comment: Nature Materials, in pres

Ariel – a window to the origin of life on early earth?

Is there life beyond Earth? An ideal research program would first ascertain how life on Earth began and then use this as a blueprint for its existence elsewhere. But the origin of life on Earth is still not understood, what then could be the way forward? Upcoming observations of terrestrial exoplanets provide a unique opportunity for answering this fundamental question through the study of other planetary systems. If we are able to see how physical and chemical environments similar to the early Earth evolve we open a window into our own Hadean eon, despite all information from this time being long lost from our planet’s geological record. A careful investigation of the chemistry expected on young exoplanets is therefore necessary, and the preparation of reference materials for spectroscopic observations is of paramount importance. In particular, the deduction of chemical markers identifying specific processes and features in exoplanetary environments, ideally “uniquely”. For instance, prebiotic feedstock molecules, in the form of aerosols and vapours, could be observed in transmission spectra in the near future whilst their surface deposits could be observed from reflectance spectra. The same detection methods also promise to identify particular intermediates of chemical and physical processes known to be prebiotically plausible. Is Ariel truly able to open a window to the past and answer questions concerning the origin of life on our planet and the universe? In this paper, we discuss aspects of prebiotic chemistry that will help in formulating future observational and data interpretation strategies for the Ariel mission. This paper is intended to open a discussion and motivate future detailed laboratory studies of prebiotic processes on young exoplanets and their chemical signatures