Temperature dependence of the pre-edge structure in the Ti K-edge x-ray absorption spectrum of rutile

11 pages, 2 figuresInternational audienceThe temperature dependence of the pre-edge features in x-ray absorption spectroscopy is reviewed. Then, the temperature dependence of the pre-edge structure at the K-edge of titanium in rutile TiO2 is measured at low and room temperature. The first two peaks grow with temperature. The fact that these two peaks also correspond to electric quadrupole transitions is explained by a recently proposed theory

Recent progress in high-pressure X-ray absorption spectroscopy studies at the ODE beamline

I.J. and A.K. are grateful to the Latvian Council of Science project no. lzp-2018/2-0353 for financial support. The research leading to these results has been partially supported by the project CALIPSOplus under the Grant Agreement No. 730872 from the EU Framework Programme for Research and Innovation HORIZON 2020.High pressure energy-dispersive X-ray absorption spectroscopy is a valuable structural technique, especially, when combined with a nano-polycrystalline diamond anvil cell. Here we present recent results obtained using the dispersive setup of the ODE beamline at SOLEIL synchrotron. The effect of pressure and temperature on the X-ray induced photoreduction is discussed on the example of nanocrystalline CuO. The possibility to follow local environment changes during pressure-induced phase transitions is demonstrated for α-MoO (Formula presented.) based on the reverse Monte Carlo simulations.Horizon 2020 project CALIPSOplus under the Grant Agreement No. 73087; Latvian Council of Science project no. lzp-2018/2-0353; Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under grant agreement No. 739508, project CAMART

"Live” Prussian blue fading by time-resolved X-ray absorption spectroscopy

Prussian blue (PB) is an artists' pigment that has been frequently used in many artworks but poses several problems of conservation because of its fading under light and anoxia treatment. PB fading is due to the reduction of iron(III) into iron(II) and depends a lot on the object investigated. Due to the complexity of the structure, the precise physico-chemical mechanisms behind the redox process remain obscure. In this paper, we present a procedure to investigate light- and anoxia-induced fading of PB-paper samples by means of time resolved X-ray absorption spectroscopy performed at the Fe K-edge. A system composed of a visible light source and a flux-controlled environmental cell allowed light, gas and humidity to be modified in situ. The synchrotron X-ray beam was evidenced to induce a reduction of PB and to play a major role in the kinetics. The analysis of the PB fading kinetics of a sample submitted to various gas and light environments showed that both synchrotron beam and anoxia were influencing PB reduction in a correlated way. In comparison, light was found to play a minor role. Finally, we have demonstrated that the type of paper substrate could influence significantly the kinetics of reduction. Several hypotheses to explain the correlation between PB reduction mechanism and substrate are presente

Detection Limits for Natural Circular Dichroism of Chiral Complexes in the X-ray Range

Whereas both Magnetic Circular Dichroism and Faraday Rotation studies have been successfully carried out at the K-, L- and M- absorption edges of metal atoms in ferromagnetic systems, Natural optical activity of chiral complexes has not yet been detected quite unambiguously in the X-ray range. We review a number of theoretical arguments which confirm that the optical asymmetry factor g(sigma) should be very small in the X-ray range for unoriented powdered samples, especially at the K-absorption edges. This stimulating challenge prompted us to start an intensive programme of measurements aimed at detecting natural circular dichroism in both the soft and ''firm'' X-ray ranges. Although some of our experiments look consistent with the presence of the expected effect, our conclusions cannot be taken yet as definitive due to the presence of a weak residual signal which, unfortunately, could not be eliminated

Les origines du rayonnement synchrotron

Les premiers synchrotrons accéléraient des protons pour la physique nucléaire. Ensuite ils furent utilisés pour accumuler et accélérer des électrons et des positrons, afin de réaliser des collisions, pour la physique des hautes énergies. Le positron est l’antiparticule de l’électron. C’est à ce moment que les synchrotrons se révélèrent être de puissantes sources de rayonnement électromagnétique qui furent depuis utilisées pour l’étude de la matière. Aujourd’hui des synchrotrons de plus en plus nombreux permettent l’étude de la matière avec des résolutions spatiales et temporelles extrêmes.The first synchrotrons served in nuclear physics to accelerate protons. They were then employed to accumulate and accelerate electrons and positrons, in order to produce collisions for high-energy physics — the positron being the antiparticle of the electron. It was at the time that synchrotrons were discovered to be strong sources of electromagnetic radiation and were turned toward the study of matter. Today, the multiplication of synchrotrons makes it possible to study matter with very high spatial and temporal resolution

Investigation of the metamagnetic transition in Y2Co7H6.

International audienceThe effects of hydrogen absorption on the crystalline and magnetic properties of the γ-phase Y2Co7H6 were examined by bulk magnetic measurements, neutron diffraction and X-ray absorption spectroscopy. An orthorhombic distortion of the unit cell occurs upon hydrogen insertion, accompanied by a reduction of the magnetic moment on Co and a decrease of the ordering temperature. Magnetic measurements indicate a metamagnetic transition occurring in the γ-phase hydride. The transition shows a broad hysteresis and the magnitude of the critical field is found to decrease with increasing temperature. The electronic structure of Co in Y2Co7 and Y2Co7H6 has been investigated by X-ray absorption spectroscopy. The observed decrease of the pre-peak intensities in the Co-K edge XANES spectra are related to the changes of the 4p–3d density of states upon hydrogen insertion. A comparative X-ray magnetic circular dichroism investigation at the Co-K edge has been carried out for Y2Co7 and Y2Co7H6. The observed XMCD signal enables us to propose that ferromagnetic ordering occurs in the γ-hydride

Real time monitoring of the evolution of Ni2+ environment in faujasite upon rehydration by in situ dispersive-EXAFS.

The evolution of both oxygen and framework tetrahedral shells around Ni2+ cations in faujasite upon rehydration can be described in real time thanks to in situ dispersive-EXAFS. Such type of analysis permits precise experimental description of the coordination environment of cations in zeolite structures under different hydration conditions

In situ XANES study of the influence of varying temperature and oxygen fugacity on iron oxidation state and coordination in a phonolitic melt

International audienceIron oxidation state and environment in magmas affect their phase diagram and their properties, including viscosity and density, which determine magma mobility and eruptive potential. In turn, magma composition, pressure, temperature and oxygen fugacity affect iron oxidation state and coordination, potentially leading to complex feedbacks associated with magma ascent, degassing and eruption. While equilibrium experiments and models have led to a deep understanding of the role of iron in melts, our knowledge of the effects of disequilibrium processes on iron oxidation state and its structural role in lavas and magmas remains limited. Accordingly, we performed a series of dynamic disequilibrium experiments on a natural melt composition (a phonolite lava from Erebus volcano, Antarctica) at atmospheric pressure, in which oxygen fugacity and temperature were controlled and varied. During the experiments, we continuously measured iron oxidation and coordination using Fe K-edge dispersive X-ray Absorption Spectroscopy (XAS). We found that iron oxidation state changes in the phonolite melt are reversible and well reproduced by existing models. Changes in iron oxidation state are driven by joint diffusion of alkali cations and oxygen anions at magmatic temperatures (~ 1000 °C for Erebus phonolite). However, redox diffusion timescales are too slow for any significant oxygen exchange with the atmosphere at the lava/air interface or via air entrainment. Turning to iron coordination, while Fe 2+ and Fe 3+ are present mostly in an average five-fold coordination, complex coordination variations decoupled from redox changes were detected. The data suggest transitions between Fe 3+ in four-fold and six-fold coordination prior to reduction or as a consequence of oxidation. This questions the possible implication of Fe coordination changes in triggering crystallisation of magnetite nanolites upon magma ascent, and, through such crystallisation events, in promoting magma explosivity

Towards quantitative magnetic information from transition metal K-edge XMCD of Prussian Blue analogs

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