Site symmetry and crystal symmetry: a spherical tensor analysis

The relation between the properties of a specific crystallographic site and the properties of the full crystal is discussed by using spherical tensors. The concept of spherical tensors is introduced and the way it transforms under the symmetry operations of the site and from site to site is described in detail. The law of spherical tensor coupling is given and illustrated with the example of the electric dipole and quadrupole transitions in x-ray absorption spectroscopy. The main application of the formalism is the reduction of computation time in the calculation of the properties of crystals by band structure methods. The general approach is illustrated by the examples of substitutional chromium in spinel and substitutional vanadium in garnet.Comment: 27 pages, 3 figure

Atomic-Scale Study of Metal–Oxide Interfaces and Magnetoelastic Coupling in Self-Assembled Epitaxial Vertically Aligned Magnetic Nanocomposites

Vertically aligned nanocomposites (VANs) of metal/oxide type have recently emerged as a novel class of heterostructures with great scientific and technological potential in the fields of nanomagnetism, multiferroism, and catalysis. One of the salient features of these hybrid materials is their huge vertical metal/oxide interface, which plays a key role in determining the final magnetic and/or transport properties of the composite structure. However, in contrast to their well‐studied planar counterparts, detailed information on the structural features of vertical interfaces encountered in VANs is scarce. In this work, high resolution scanning transmission electron microscopy (STEM) and electron energy‐loss spectroscopy (EELS) are used to provide an element selective atomic‐scale analysis of the interface in a composite consisting of ultrathin, self‐assembled Ni nanowires, vertically epitaxied in a SrTiO3/SrTiO3(001) matrix. Spectroscopic EELS measurements evidence rather sharp interfaces (6–7 Å) with the creation of metallic NiTi bonds and the absence of nickel oxide formation is confirmed by X‐ray absorption spectroscopy measurements. The presence of these well‐defined phase boundaries, combined with a large lattice mismatch between the oxide and metallic species, gives rise to pronounced magnetoelastic effects. Self‐assembled columnar Ni:SrTiO3 composites thus appear as ideal model systems to explore vertical strain engineering in metal/oxide nanostructures

Collective magnetotaxis of microbial holobionts is optimized by the three-dimensional organization and magnetic properties of ectosymbionts

International audienceOver the last few decades, symbiosis and the concept of holobiont—a host entity with a population of symbionts—have gained a central role in our understanding of life functioning and diversification. Regardless of the type of partner interactions, understanding how the biophysical properties of each individual symbiont and their assembly may generate collective behaviors at the holobiont scale remains a fundamental challenge. This is particularly intriguing in the case of the newly discovered magnetotactic holobionts (MHB) whose motility relies on a collective magnetotaxis (i.e., a magnetic field-assisted motility guided by a chemoaerotaxis system). This complex behavior raises many questions regarding how magnetic properties of symbionts determine holobiont magnetism and motility. Here, a suite of light-, electron- and X-ray-based microscopy techniques [including X-ray magnetic circular dichroism (XMCD)] reveals that symbionts optimize the motility, the ultrastructure, and the magnetic properties of MHBs from the microscale to the nanoscale. In the case of these magnetic symbionts, the magnetic moment transferred to the host cell is in excess (10 2 to 10 3 times stronger than free-living magnetotactic bacteria), well above the threshold for the host cell to gain a magnetotactic advantage. The surface organization of symbionts is explicitly presented herein, depicting bacterial membrane structures that ensure longitudinal alignment of cells. Magnetic dipole and nanocrystalline orientations of magnetosomes were also shown to be consistently oriented in the longitudinal direction, maximizing the magnetic moment of each symbiont. With an excessive magnetic moment given to the host cell, the benefit provided by magnetosome biomineralization beyond magnetotaxis can be questioned

Tracking the signature of low symmetry environments in the XAS K pre-edge

For Co-containing crystalline compounds measured by XAS, the influence of the local symmetry on the K pre -edge features is studied using advanced Ligand Field Multiplet (LFM) calculations, which accurately take into account the p -d hybridization. The LFM theory is used to calculate the K pre -edge spectra of Co2+ in various environments and the absolute intensities of electric -quadrupole and -dipole transitions involved in the pre -edge. This enables to reproduce the spectra for cubic (Oh, Td) and lower symmetries (C D3h), and allows quantitative derivation of the local p -d mixing

1s2p resonant inelastic x-ray scattering-magnetic circular dichroism: A sensitive probe of 3d magnetic moments using hard x-ray photons

International audienceWe investigated the magnetic properties of thin magnetite and iron films grown on MgO(001) by means of hard x-ray photon-in photon-out probe, namely, 1s2p resonant inelastic x-ray scattering-magnetic circular dichroism (RIXS-MCD). A comparison of the spectra acquired from bulk and thin layer magnetite samples reveals their nearly identical shape. Hysteresis loops measured with RIXS-MCD also show a close similarity to the vibrating sample magnetometer profiles supporting the conclusion that the technique can be applied for the quantitative analysis of element and site specific magnetization in buried films containing transition metal elements. We show that Fe 1s2p RIXS-MCD is insensitive to the magnetic signal of iron impurities naturally dispersed in monocrystalline MgO substrates. The latter, combined with a unique feature of resonant inelastic x-ray scattering, namely the ability to tune incident and emitted photon (transfer) energy, allows us to separate the dichroic signal of metal layers from that of ferrite and, thus, to independently probe the magnetization of metal and oxide layers in multilayer system

V oxidation state in Fe-Ti oxides by high-energy resolution fluorescence-detected X-ray absorption spectroscopy

The oxidation state of vanadium in natural and synthetic Fe-Ti oxides is determined using high-energy resolution fluorescence-detected X-ray absorption spectroscopy (HERFD-XAS). Eleven natural magnetite-bearing samples from a borehole of the Main Magnetite Layer of the Bushveld Complex (South Africa), five synthetic Fe oxide samples, and three natural hematite-bearing samples from Dharwar supergroup (India) are investigated. V K edge spectra were recorded on the ID26 beamline at the European Synchrotron Radiation Facility (Grenoble, France), and the pre-edge features were used to determine the local environment and oxidation state of vanadium. In the case of the magnetite samples (natural and synthetic), we show that vanadium is incorporated in the octahedral site of the spinel structure under two oxidation states: +III and +IV. The variations of the pre-edge area are interpreted as various proportions in V3+ and V4+ (between 9.5 and 16.3% of V4+), V3+ being the main oxidation state. In particular, the variations of the V4+/V3+ ratio along the profile of the Main Magnetite Layer seem to follow the crystallization sequence of the layer. In the case of the hematite samples from India, the pre-edge features indicate that vanadium is substituted to Fe and mainly incorporated as V4+ (between 40 and 72% of V4+). We also demonstrate the potentiality of HERFD-XAS for mineralogical studies, since it can filter out the unwanted fluorescence and give better resolved spectra than conventional XAS

X-ray magnetic and natural circular dichroism from first principles: Calculation of K- and L-1-edge spectra

An efficient first-principles approach to calculate x-ray magnetic circular dichroism (XMCD) and x-ray natural circular dichroism (XNCD) is developed and applied in the near-edge region at the K and L-1 edges in solids. Computation of circular dichroism requires precise calculations of x-ray absorption spectra (XAS) for circularly polarized light. For the derivation of the XAS cross section, we used a relativistic description of the photon-electron interaction that results in an additional term in the cross section that couples the electric dipole operator with an operator sigma . (is an element of x r) that we call the spin position operator. The numerical method relies on pseudopotentials, on the gauge including projected augmented-wave method, and on a collinear spin relativistic description of the electronic structure. We apply the method to calculations of K-edge XMCD spectra of ferromagnetic iron, cobalt, and nickel and of I L-1-edge XNCD spectra of alpha-LiIO3, a compound with broken inversion symmetry. For XMCD spectra we find that, even if the electric dipole term is the dominant one, the electric quadrupole term is not negligible (8% in amplitude in the case of iron). The term coupling the electric dipole operator with the spin-position operator is significant (28% in amplitude in the case of iron). We obtain a sum rule relating this term to the spin magnetic moment of the p states. In alpha-LiIO3 we recover the expected angular dependence of the XNCD spectra