A series of asymmetrically substituted free-base di- and tetra-phenylporphyrins and the associated Zn-phenylporphyrins were synthesized and studied by X-ray diffraction, NMR, infrared, electronic absorption spectra, as well as fluorescence emission spectroscopy, along with theoretical simulations of the electronic and vibration structures. The synthesis selectively afforded trans-A₂B₂ porphyrin...

X-ray emission spectra recorded in the off-resonant regime carry information on the density of unoccupied states. It is known that by employing the Kramers-Heisenberg formalism, the high energy resolution off-resonant spectroscopy (HEROS) is equivalent to the x-ray absorption spectroscopy (XAS) technique and provides the same electronic state information. Moreover, in the present Letter we demo...

The fluorescence-detection techniques of cosmic-ray air-shower experiments require precise knowledge of atmospheric properties to reconstruct air-shower energies. Up to now, the atmosphere in desert-like areas was assumed to be stable enough so that occasional calibration of atmospheric attenuation would suffice to reconstruct shower profiles. However, serious difficulties have been reported in...

The objective of this article is to describe the capability of a two-dimensional (2D) approach to X-ray absorption near-edge structure (XANES) measurement by means of a partial fluorescence yield (PFY) method. 2D-XANES measurements were achieved by using a silicon drift detector as an energy-dispersive fluorescence detector. The advantage of this technique is that it allows full surveys of X-ra...

Fluorescence yield (FY) detected x-ray absorption spectra (XAS) of 3d transition metal ions are calculated from the integrated 2p3d resonant x-ray emission spectra. The resulting FY-XAS spectra are compared with the normal XAS spectra corresponding to the absorption cross section and significant deviations between the two spectra are found. This implies that the assumption that the FY-XAS spect...

In energy dispersive X-ray fluorescence analysis, the estimation and removal of the continuum on which the X-ray spectrum is superimposed is a primary requirement. The algorithms commonly used are either complex, or in the case of, e.g., neural network algorithms, computation-intensive. They usually require strong constraints and/or hypotheses on the data or the shape of the continuum. Moreover...

L-edge soft X-ray spectroscopy has been proven to be a powerful tool to unravel the peculiarities of electronic structure of transition metal compounds in solution. However, the X-ray absorption spectrum is often probed in the total or partial fluorescence yield modes, what leads to inherent distortions with respect to the true transmission spectrum. In the present work, we combine photon- and ...

Nafion contamination by ferrous-alloy corrosion products, resulting in dramatic drops of the Ohmic potential, is a suspected major failure mode of polymer electrolyte membrane fuel cells that make use of metallic bipolar plates. This study demonstrates the potential of scanning transmission X-ray microscopy combined with X-ray absorption and fluorescence microspectroscopy for exploring corrosio...

XANES and EXAFS information is conventionally measured in transmission through the energy-dependent absorption of X-rays or by observing X-ray fluorescence, but secondary fluorescence processes, such as the emission of electrons and optical photons (e.g., 200-1000 nm), can also be used as a carrier of the XAS signatures, providing complementary information such as improved surface specificity. ...