Femtosecond X-ray emission study of the spin cross-over dynamics in haem proteins

In haemoglobin (consisting of four globular myoglobin-like subunits), the change from the low-spin (LS) hexacoordinated haem to the high spin (HS) pentacoordinated domed form upon ligand detachment and the reverse process upon ligand binding, represent the transition states that ultimately drive the respiratory function. Visible-ultraviolet light has long been used to mimic the ligand release from the haem by photodissociation, while its recombination was monitored using time-resolved infrared to ultraviolet spectroscopic tools. However, these are neither element- nor spin-sensitive. Here we investigate the transition state in the case of Myoglobin-NO (MbNO) using femtosecond Fe Kalpha and Kbeta non-resonant X-ray emission spectroscopy (XES) at an X-ray free-electron laser upon photolysis of the Fe-NO bond. We find that the photoinduced change from the LS (S = 1/2) MbNO to the HS (S = 2) deoxy-myoglobin (deoxyMb) haem occurs in ca. 800 fs, and that it proceeds via an intermediate (S = 1) spin state. The XES observables also show that upon NO recombination to deoxyMb, the return to the planar MbNO ground state is an electronic relaxation from HS to LS taking place in ca. 30 ps. Thus, the entire ligand dissociation-recombination cycle in MbNO is a spin cross-over followed by a reverse spin cross-over process

Hard x-ray emission spectroscopy: a powerful tool for the characterization of magnetic semiconductors

This review aims to introduce the x-ray emission spectroscopy (XES) and resonant inelastic x-ray scattering (RIXS) techniques to the materials scientist working with magnetic semiconductors (e.g. semiconductors doped with 3d transition metals) for applications in the field of spin-electronics. We focus our attention on the hard part of the x-ray spectrum (above 3 keV) in order to demonstrate a powerful element- and orbital-selective characterization tool in the study of bulk electronic structure. XES and RIXS are photon-in/photon-out second order optical processes described by the Kramers-Heisenberg formula. Nowadays, the availability of third generation synchrotron radiation sources permits applying such techniques also to dilute materials, opening the way for a detailed atomic characterization of impurity-driven materials. We present the K{\beta} XES as a tool to study the occupied valence states (directly, via valence-to-core transitions) and to probe the local spin angular momentum (indirectly, via intra-atomic exchange interaction). The spin sensitivity is employed, in turn, to study the spin-polarized unoccupied states. Finally, the combination of RIXS with magnetic circular dichroism (RIXS-MCD) extends the possibilities of standard magnetic characterization tools.Comment: Topical review (17 pages, 13 figures, 188 references). This is an author-created, un-copyedited version of an article accepted for publication in Semiconductor Science and Technology. IOP Publishing Ltd is not responsible for any errors or omissions in this version of the manuscript or any version derived from i

XAFS analyses of molten metal fluorides

X-ray absorption fine structure studies of molten metal fluorides containing the materials related to nuclear engineering are intensively summarized. By using XAFS spectra data of divalent and trivalent cation metal fluorides in molten state which have been collected by authors’ group for a few years, local structure have been extracted and discussed systematically in conjunction with other spectroscopic studies and numerical calculations. In molten divalent fluorides, tetrahedral coordination of fluorides around a cation is predominant. In the case of pure molten trivalent fluorides, structure with more than 6-coordination has been suggested in some cases, but octahedral coordination structure is much stabilized at heavier rare earth metal fluorides. By mixing with alkali metal fluorides, it is a general trend that inter-ionic distances keep constant, but coordination number of fluorides decreases. In experimental chapter, all the details of sample preparation, furnace installation, X-ray optics setups and data analyses procedures are explained. Finally, future expectations of XAFS technique are also suggested

Resonant Elastic Soft X-Ray Scattering

Resonant (elastic) soft x-ray scattering (RSXS) offers a unique element, site, and valence specific probe to study spatial modulations of charge, spin, and orbital degrees of freedom in solids on the nanoscopic length scale. It cannot only be used to investigate single crystalline materials. This method also enables to examine electronic ordering phenomena in thin films and to zoom into electronic properties emerging at buried interfaces in artificial heterostructures. During the last 20 years, this technique, which combines x-ray scattering with x-ray absorption spectroscopy, has developed into a powerful probe to study electronic ordering phenomena in complex materials and furthermore delivers important information on the electronic structure of condensed matter. This review provides an introduction to the technique, covers the progress in experimental equipment, and gives a survey on recent RSXS studies of ordering in correlated electron systems and at interfaces