Yves Joly

Self-consistent aspects of x-ray absorption calculations

We implemented a self-consistent, real-space x-ray absorption calculation within the FDMNES code. We performed the self-consistency within several schemes and identified which one is the most appropriate. We show a method that allows a rigorous setting of the Fermi level and thus an estimation of the energy cutoff for the identification and elimination of the occupied states. We investigated what are the structures where one can afford performing the self-consistent calculation at a lesser cluster radius than the absorption one. We exemplify the effects of the self-consistency at the K-edge and for several reference cases, including the copper Cu and the rutile TiO(2). We verified the robustness of our procedure on the transitional 3d and 4d elements. Although amelioration can be noticed, the self-consistency performed at the K-edge does not bring a major improvement of the calculated spectra. Taking into consideration a non-self-consistent, non-spherical potential gives better results than a self-consistent muffin-tin approximation calculation.

Optimized Finite Difference Method for the Full-Potential XANES Simulations: Application to Molecular Adsorption Geometries in MOFs and Metal–Ligand Intersystem Crossing Transients

Accurate modeling of the X-ray absorption near-edge spectra (XANES) is required to unravel the local structure of metal sites in complex systems and their structural changes upon chemical or light stimuli. Two relevant examples are reported here concerning the following: (i) the effect of molecular adsorption on 3d metals hosted inside metal-organic frameworks and (ii) light induced dynamics of spin crossover in metal-organic complexes. In both cases, the amount of structural models for simulation can reach a hundred, depending on the number of structural parameters. Thus, the choice of an accurate but computationally demanding finite difference method for the ab initio X-ray absorption simulations severely restricts the range of molecular systems that can be analyzed by personal computers. Employing the FDMNES code [Phys. Rev. B, 2001, 63, 125120] we show that this problem can be handled if a proper diagonalization scheme is applied. Due to the use of dedicated solvers for sparse matrices, the calculation time was reduced by more than 1 order of magnitude compared to the standard Gaussian method, while the amount of required RAM was halved. Ni K-edge XANES simulations performed by the accelerated version of the code allowed analyzing the coordination geometry of CO and NO on the Ni active sites in CPO-27-Ni MOF. The Ni-CO configuration was found to be linear, while Ni-NO was bent by almost 90°. Modeling of the Fe K-edge XANES of photoexcited aqueous [Fe(bpy)3](2+) with a 100 ps delay we identified the Fe-N distance elongation and bipyridine rotation upon transition from the initial low-spin to the final high-spin state. Subsequently, the X-ray absorption spectrum for the intermediate triplet state with expected 100 fs lifetime was theoretically predicted.

Resonant X-Ray Diffraction Studies on the Charge Ordering in Magnetite

Here we show that the low temperature phase of magnetite is associated with an effective, although fractional, ordering of the charge. Evidence and a quantitative evaluation of the atomic charges are achieved by using resonant x-ray diffraction (RXD) experiments whose results are further analyzed with the help of ab initio calculations of the scattering factors involved. By confirming the results obtained from x-ray crystallography we have shown that RXD is able to probe quantitatively the electronic structure in very complex oxides, whose importance covers a wide domain of applications.

Structural and electronic evolution of the As(OH)3 molecule in high temperature aqueous solutions: An x-ray absorption investigation

The geometrical and electronic structure of the arsenious acid molecule As(OH)(3) in aqueous solutions has been investigated by x-ray absorption spectroscopy (XAS) within extended x-ray absorption spectroscopy (EXAFS) and x-ray absorption near edge structure (XANES), using realistic first-principle calculations in the latter case. This investigation was performed on aqueous solutions of arsenious acid from ambient to supercritical conditions (P = 250 and 600 bars, T <or= 500 degrees C) using a new optical cell. The analysis of the XAS spectra is consistent with (1) a constant As-O distance, (2) an opening of the O-As-O angles within the C(3V) pyramidal structure in the range 30-200 degrees C. This structural evolution comes along with a small decrease of the partial charges of the atoms in the As(OH)(3) molecule. The explanation invoked for both structural and electronic modifications observed is the weakening of the interactions, through hydrogen bonds, between the As(OH)(3) complex and water molecules. This is a fingerprint of the similar weakening of hydrogen bonding interactions in the solvent itself.

Calculating X-ray absorption near-edge structure at very low energy.

The measurement and calculation of X-ray absorption near-edge structure at very low energy can provide important information about a metallic center in biological compounds. A rapid overview of the biological applications of this technique is given, then a new method of calculating the spectra is presented. This technique, based on the use of the finite-difference method to solve the Schrödinger equation, is especially precise and potentially applicable to metalloproteins. Examples of its use on an oxide and an organic compound illustrate the kind of spectroscopic information that can be obtained.

Monitoring Morphology and Hydrogen Coverage of Nanometric Pt/γ-Al2O3 Particles by In Situ HERFD–XANES and Quantum Simulations†

Platinum nanoclusters highly dispersed on γ-alumina are widely used as heterogeneous catalysts. To understand the chemical interplay between the Pt nanoparticles, the support, and the reductive atmosphere, we performed X-ray absorption near edge structure (XANES) in situ experiments recorded in high energy resolution fluorescence detection (HERFD) mode. Spectra are assigned by comparison with simulated XANES spectra on models obtained by molecular dynamics (DFT-MD). We propose platinum cluster morphologies and quantify the hydrogen coverages compatible with XANES spectra recorded at variable hydrogen pressures and temperatures. Using cutting-edge methodologies to assign XANES spectra, this work gives unequalled atomic insights into the characterization of supported nanoclusters.

Surface Science Approach to the Solid–Liquid Interface: Surface‐Dependent Precipitation of Ni(OH)2 on α‐Al2O3 Surfaces

Surface-dependent precipitation: The adsorption of Ni(II) complexes in aqueous solution on (0001) and (1102) α-Al(2)O(3) single-crystal surfaces has been studied (see the X-ray absorption spectra obtained for parallel and perpendicular polarization directions). The use of planar model systems emphasizes the crucial role of the Al(2)O(3) orientation for Ni dispersion with practical implications in catalyst preparation procedures.

X-ray scattering study of the order parameters in multiferroic TbMnO3

We report on an extensive investigation of the multiferroic compound TbMnO3 using x-ray scattering techniques. Nonresonant x-ray magnetic scattering NRXMS was used to characterize the domain population of the single crystal used in our experiments. This revealed that the dominant domain is overwhelmingly A type. The temperature dependence of the intensity and wave vector associated with the incommensurate magnetic order was found to be in good agreement with neutron scattering data. X-ray resonant scattering experiments were performed in the vicinity of the Mn K and Tb L3 edges in the high-temperature collinear phase, the intermediate temperature cycloidal and ferroelectric phase, and the low-temperature phase. In the collinear phase, where according to neutron diffraction only the Mn sublattice is ordered, resonant E1-E1 satellites were found at the Mn K edge associated with A-type but also F-type peaks. Detailed measurements of the azimuthal dependence of the F-type satellites and their absence in the NRXMS experiments leads us to conclude that they are most likely nonmagnetic in origin. We suggest instead that they may be associated with an induced charge multipole. At the Tb L3 edge, resonant A- and F-type satellites were observed in the collinear phase again associated with E1-E1 events. We attribute these to a polarization of the Tb 5d states by the ordering of the Mn sublattice. On cooling into the cycloidal and ferroelectric phase, a new set of resonant satellites appear corresponding to C-type order. These appear at the Tb L3 edge only. In addition to a dominant E1-E1 component in the - channel, a weaker component is found in the preedge with - polarization and displaced by −7 eV with respect to the E1-E1 component. Comprehensive calculations of the x-ray scattering cross section were performed using the FDMNES code. These calculations show that the unrotated - component of the Tb L3 C-type peaks appearing in the ferroelectric phase contains a contribution from a multipole that is odd with respect to both space and time, known in various contexts as the anapole. Our experiments thus provide tentative evidence for the existence of a type of anapolar order parameter in the rare-earth manganite class of mulitferroic compounds.

Emergence of ferromagnetism and Jahn-Teller distortion in LaMn1−xCrxO3 (x < 0.15)

The emergence of a ferromagnetic component in LaMnO3 with low Cr-for-Mn substitution has been studied by x-ray absorption spectroscopy and x-ray magnetic circular dichroism at the Mn and Cr K edges. The local magnetic moment strength for the Mn and Cr are proportional to each other and follows the macroscopic magnetization. The net ferromagnetic components of Cr3+ and Mn3+ are found antiferromagnetically coupled. Unlike hole doping by La site substitution, the inclusion of Cr3+ ions up to x = 0.15 does not decrease the Jahn-Teller (JT) distortion and consequently does not signi cantly a ect the orbital ordering. This demonstrates that the emergence of the ferromagnetism is not related to JT weakening and likely arises from a complex orbital mixing.

Antiferromagnetically spin polarized oxygen observed in magnetoelectric TbMn2O5.

We report the direct measurement of antiferromagnetic spin polarization at the oxygen sites in the multiferroic TbMn2O5, through resonant soft x-ray magnetic scattering. This supports recent theoretical models suggesting that the oxygen spin polarization is key to the magnetoelectric coupling mechanism. The spin polarization is observed through a resonantly enhanced diffraction signal at the oxygen K edge at the commensurate antiferromagnetic wave vector. Using the fdmnes code we have accurately reproduced the experimental data. We have established that the resonance arises through the spin polarization on the oxygen sites hybridized with the square based pyramid Mn3+ ions. Furthermore we have discovered that the position of the Mn3+ ion directly influences the oxygen spin polarization.