Non-d0d^0 Mn-driven ferroelectricity in antiferromagnetic BaMnO3_3

Using first-principles density functional theory we predict a ferroelectric ground state -- driven by off-centering of the magnetic Mn$^{4+}$ ion -- in perovskite-structure BaMnO$_3$. Our finding is surprising, since the competition between energy-lowering covalent bond formation, and energy-raising Coulombic repulsions usually only favors off-centering on the perovskite $B$-site for non-magnetic $d^0$ ions. We explain this tendency for ferroelectric off-centering by analyzing the changes in electronic structure between the centrosymmetric and polar states, and by calculating the Born effective charges; we find anomalously large values for Mn and O consistent with our calculated polarization of 12.8 $\mu$C/cm$^2$. Finally, we suggest possible routes by which the perovskite phase may be stabilized over the usual hexagonal phase, to enable a practical realization of a single-phase multiferroic.Comment: 6 pages, 3 figure

Normal Mode Determination of Perovskite Crystal Structures with Octahedral Rotations: Theory and Applications

Nuclear site analysis methods are used to enumerate the normal modes of $ABX_{3}$ perovskite polymorphs with octahedral rotations. We provide the modes of the fourteen subgroups of the cubic aristotype describing the Glazer octahedral tilt patterns, which are obtained from rotations of the $BX_{6}$ octahedra with different sense and amplitude about high symmetry axes. We tabulate all normal modes of each tilt system and specify the contribution of each atomic species to the mode displacement pattern, elucidating the physical meaning of the symmetry unique modes. We have systematically generated 705 schematic atomic displacement patterns for the normal modes of all 15 (14 rotated + 1 unrotated) Glazer tilt systems. We show through some illustrative examples how to use these tables to identify the octahedral rotations, symmetric breathing, and first-order Jahn-Teller anti-symmetric breathing distortions of the $BX_{6}$ octahedra, and the associated Raman selection rules. We anticipate that these tables and schematics will be useful in understanding the lattice dynamics of bulk perovskites and would serve as reference point in elucidating the atomic origin of a wide range of physical properties in synthetic perovskite thin films and superlattices.Comment: 17 pages, 3 figures, 17 tables. Supporting information accessed through link specified within manuscrip

Strain-controlled band engineering and self-doping in ultrathin LaNiO3_3 films

We report on a systematic study of the temperature-dependent Hall coefficient and thermoelectric power in ultra-thin metallic LaNiO$_3$ films that reveal a strain-induced, self-doping carrier transition that is inaccessible in the bulk. As the film strain varies from compressive to tensile at fixed composition and stoichiometry, the transport coefficients evolve in a manner strikingly similar to those of bulk hole-doped superconducting cuprates with varying doping level. Density functional calculations reveal that the strain-induced changes in the transport properties are due to self-doping in the low-energy electronic band structure. The results imply that thin-film epitaxy can serve as a new means to achieve hole-doping in other (negative) charge-transfer gap transition metal oxides without resorting to chemical substitution

Worker remittances and the global preconditions of ‘smart development’

With the growing environmental crisis affecting our globe, ideas to weigh economic or social progress by the ‘energy input’ necessary to achieve it are increasingly gaining acceptance. This question is intriguing and is being dealt with by a growing number of studies, focusing on the environmental price of human progress. Even more intriguing, however, is the question of which factors of social organization contribute to a responsible use of the resources of our planet to achieve a given social result (‘smart development’). In this essay, we present the first systematic study on how migration – or rather, more concretely, received worker remittances per GDP – helps the nations of our globe to enjoy social and economic progress at a relatively small environmental price. We look at the effects of migration on the balance sheets of societal accounting, based on the ‘ecological price’ of the combined performance of democracy, economic growth, gender equality, human development, research and development, and social cohesion. Feminism in power, economic freedom, population density, the UNDP education index as well as the receipt of worker remittances all significantly contribute towards a ‘smart overall development’, while high military expenditures and a high world economic openness are a bottleneck for ‘smart overall development’

Advances in ab-initio theory of Multiferroics. Materials and mechanisms: modelling and understanding

Within the broad class of multiferroics (compounds showing a coexistence of magnetism and ferroelectricity), we focus on the subclass of "improper electronic ferroelectrics", i.e. correlated materials where electronic degrees of freedom (such as spin, charge or orbital) drive ferroelectricity. In particular, in spin-induced ferroelectrics, there is not only a {\em coexistence} of the two intriguing magnetic and dipolar orders; rather, there is such an intimate link that one drives the other, suggesting a giant magnetoelectric coupling. Via first-principles approaches based on density functional theory, we review the microscopic mechanisms at the basis of multiferroicity in several compounds, ranging from transition metal oxides to organic multiferroics (MFs) to organic-inorganic hybrids (i.e. metal-organic frameworks, MOFs)Comment: 22 pages, 9 figure

Control of magnetic anisotropy by orbital hybridization in (La0.67Sr0.33MnO3)n/(SrTiO3)n superlattice

The asymmetry of chemical nature at the hetero-structural interface offers an unique opportunity to design desirable electronic structure by controlling charge transfer and orbital hybridization across the interface. However, the control of hetero-interface remains a daunting task. Here, we report the modulation of interfacial coupling of (La0.67Sr0.33MnO3)n/(SrTiO3)n superlattices by manipulating the periodic thickness with n unit cells of SrTiO3 and n unit cells La0.67Sr0.33MnO3. The easy axis of magnetic anisotropy rotates from in-plane (n = 10) to out-of-plane (n = 2) orientation at 150 K. Transmission electron microscopy reveals enlarged tetragonal ratio > 1 with breaking of volume conservation around the (La0.67Sr0.33MnO3)n/(SrTiO3)n interface, and electronic charge transfer from Mn to Ti 3d orbitals across the interface. Orbital hybridization accompanying the charge transfer results in preferred occupancy of 3d3z2-r2 orbital at the interface, which induces a stronger electronic hopping integral along the out-of-plane direction and corresponding out-of-plane magnetic easy axis for n = 2. We demonstrate that interfacial orbital hybridization in superlattices of strongly correlated oxides may be a promising approach to tailor electronic and magnetic properties in device applications

Quantum sensing of magnetic fields with molecular color centers

Molecular color centers, such as $S=1$ Cr($o$-tolyl)$_{4}$, show promise as an adaptable platform for magnetic quantum sensing. Their intrinsically small size, i.e., 1-2 nm, enables them to sense fields at short distances and in various geometries. This feature, in conjunction with tunable optical read-out of spin information, offers the potential for molecular color centers to be a paradigm shifting materials class beyond diamond-NV centers by accessing a distance scale opaque to NVs. This capability could, for example, address ambiguity in the reported magnetic fields arising from two-dimensional magnets by allowing for a single sensing technique to be used over a wider range of distances. Yet, so far, these abilities have only been hypothesized with theoretical validation absent. We show through simulation that Cr($o$-tolyl)$_{4}$ can spatially resolve proximity-exchange versus direct magnetic field effects from monolayer CrI$_{3}$ by quantifying how these interactions impact the excited states of the molecule. At short distances, proximity exchange dominates through molecule-substrate interactions, but at further distances the molecule behaves as a typical magnetic sensor, with magnetostatic effects dominating changes to the energy of the excited state. Our models effectively demonstrate how a molecular color center could be used to measure the magnetic field of a 2D magnet and the role different distance-dependent interactions contribute to the measured field.Comment: 7 pages, 4 figure