Virginie Simonet

The Role of Order-Disorder Transitions in the Quest for Molecular Multiferroics: Structural and Magnetic Neutron Studies of a Mixed Valence Iron (II)-Iron (III) Formate Framework

Neutron diffraction studies have been carried out to shed light on the unprecedented order-disorder phase transition (ca. 155 K) observed in the mixed-valence iron(II)-iron(III) formate framework compound [NH(2)(CH(3))(2)](n)[Fe(III)Fe(II)(HCOO)(6)](n). The crystal structure at 220 K was first determined from Laue diffraction data, then a second refinement at 175 K and the crystal structure determination in the low temperature phase at 45 K were done with data from the monochromatic high resolution single crystal diffractometer D19. The 45 K nuclear structure reveals that the phase transition is associated with the order-disorder of the dimethylammonium counterion that is weakly anchored in the cavities of the [Fe(III)Fe(II)(HCOO)(6)](n) framework. In the low-temperature phase, a change in space group from P31c to R3c occurs, involving a tripling of the c-axis due to the ordering of the dimethylammonium counterion. The occurrence of this nuclear phase transition is associated with an electric transition, from paraelectric to antiferroelectric. A combination of powder and single crystal neutron diffraction measurements below the magnetic order transition (ca. 37 K) has been used to determine unequivocally the magnetic structure of this Néel N-Type ferrimagnet, proving that the ferrimagnetic behavior is due to a noncompensation of the different Fe(II) and Fe(III) magnetic moments.

Magnetic frustration in an iron-based Cairo pentagonal lattice.

The Fe3+ lattice in the Bi2Fe4O9 compound is found to materialize the first analogue of a magnetic pentagonal lattice. Because of its odd number of bonds per elemental brick, this lattice, subject to first neighbor antiferromagnetic interactions, is prone to geometric frustration. The Bi2Fe4O9 magnetic properties have been investigated by macroscopic magnetic measurements and neutron diffraction. The observed noncollinear magnetic arrangement is related to the one stabilized on a perfect tiling as obtained from a mean field analysis with direct space magnetic configuration calculations. The peculiarity of this structure arises from the complex connectivity of the pentagonal lattice, a novel feature compared to the well-known case of triangle-based lattices.

Short-range order in undercooled Co melts

It was suggested in 1952 by Frank that an icosahedral short-range order (SRO) should be energetically favourable in undercooled melts of systems consisting of atoms with a sphere-like geometrical symmetry. Although this idea is nearly 50 years old, there is still a lack of direct experimental information on the SRO prevailing in undercooled metallic liquids. In this work the results of investigations of the SRO of deeply undercooled liquids of Co by energy dispersive diffraction of synchrotron radiation are presented. The experimentally determined structure factors were simulated by assuming that the liquid consists of clusters with different short-range structures. The best fit of the experimental data is obtained if an icosahedral SRO is assumed. Thus, our investigations strongly support Franks idea of an icosahedral SRO prevailing in undercooled metallic liquids.

Single domain magnetic helicity and triangular chirality in structurally enantiopure Ba3NbFe3Si2O14.

A novel doubly chiral magnetic order is found in the structurally chiral langasite compound Ba3NbFe3Si2O14. The magnetic moments are distributed over planar frustrated triangular lattices of triangle units. On each of these they form the same triangular configuration. This ferrochiral arrangement is helically modulated from plane to plane. Unpolarized neutron scattering on a single crystal associated with spherical neutron polarimetry proved that a single triangular chirality together with a single helicity is stabilized in an enantiopure crystal. A mean-field analysis allows us to discern the relevance on this selection of a twist in the plane to plane super-superexchange paths.

Short-range order in undercooled and stable melts forming quasicrystals and approximants and its influence on nucleation

An icosahedral short-range order has been predicted to prevail in undercooled metallic melts. For melts of pure metals, this hypothesis was recently experimentally confirmed by diffraction experiments. This paper presents results of neutron scattering experiments on the short-range order of stable and undercooled liquids of alloys forming quasicrystals and polytetrahedral crystals. The studies indicate that an icosahedral topological short-range order prevails in all of the investigated melts. The influence of this icosahedral short-range order on the nucleation behaviour of solid phases from the undercooled liquid is discussed.

Nonmagnetic insulator state in Na1CoO2 and phase separation of na vacancies.

Crystallographic, magnetic, and NMR properties of a Na1CoO2 single crystal with x approximately = 1 are presented. We identify the stoichiometric Na1CoO2 phase, which is shown to be a nonmagnetic insulator, as expected for homogeneous planes of Co3+ ions with S = 0. In addition, we present evidence that, because of slight average Na deficiency, chemical and electronic phase separation leads to a segregation of Na vacancies into the well-defined, magnetic, Na0.8CoO2 phase. The importance of phase separation is discussed in the context of magnetic order for x approximately = 0.8 and the occurrence of a metal-insulator transition for x --> 1.

Short-range order in undercooled melts forming quasicrystals and approximants

Abstract For the first time, the short-range order of deeply undercooled liquids of alloys forming quasicrystalline and polytetrahedral phases (Al13Fe4 and Al74Co26) is investigated by combining the containerless processing technique of electromagnetic levitation with elastic neutron scattering. The experimentally determined structure factor, S(Q), was simulated by assuming that clusters with different structures exist in the liquid. The best fit of the experimental data is obtained under the assumption of an icosahedral short-range order. This supports the nearly 50 year-old prediction of Frank that an icosahedral short-range order prevails in undercooled metallic liquids.

Spin-liquid correlations in the Nd-langasite anisotropic kagomé antiferromagnet.

Dynamical magnetic correlations in the geometrically frustrated Nd(3)Ga(5)SiO(14) compound were probed by inelastic neutron scattering on a single crystal. A scattering signal with a ring shape distribution in reciprocal space and unprecedented dispersive features was discovered. Comparison with calculated static magnetic scattering from models of correlated spins suggests that the observed phase is a spin liquid inherent to an antiferromagnetic kagomé-like lattice of anisotropic Nd moments.

Role of Antisymmetric Exchange in Selecting Magnetic Chirality in Ba3NbFe3Si2O14

We present an electron spin resonance (ESR) investigation of the acentric Ba(3)NbFe(3)Si(2)O(14), featuring a unique single-domain double-chiral magnetic ground state. Combining simulations of the ESR linewidth anisotropy and the antiferromagnetic-resonance modes allows us to single out the Dzyaloshinsky-Moriya (DM) interaction as the leading magnetic anisotropy term. We demonstrate that the rather minute out-of-plane DM component d(c)=45 mK is responsible for selecting a unique ground state, which endures thermal fluctuations up to astonishingly high temperatures.

Magnetic frustration on a Kagomé lattice in R3Ga5SiO14 langasites with R = Nd, Pr

In the R3Ga5SiO14 compounds, the network R of rare earth cations forms well separated planes of corner sharing triangles topologically equivalent to a Kagome lattice. Powder samples and single crystals with R = Nd and Pr were prepared and magnetostatic measurements were performed under magnetic field up to 10 T in the temperature range from 1.6 to 400 K. Analysis of the magnetic susceptibility at the high temperatures where only the quadrupolar term of the crystal electric field prevails suggests that the Nd and Pr magnetic moments can be modelled as coplanar elliptic rotators perpendicular to the threefold axis of the crystal structure that interact antiferromagnetically. Nonetheless, a disordered phase that can be ascribed to geometric frustration persists down to the lowest temperature, which is about 25 times smaller than the energy scale for the exchange interactions.