Origin of dark-channel X-ray fluorescence from transition-metal ions in water.

The nonradiative dark channels in the L-edge fluorescence spectra from transition-metal aqueous solution identify the ultrafast charge-transfer processes playing an important role in many biological and chemical systems. Yet, the exact origin of such spectral dips with respect to the X-ray transmission spectrum has remained unclear. In the present study we explore the nature of the underlying decay mechanism of 2p core-excited Co(2+) in water by probing the nonradiative Auger-type electron emission channel using photoelectron spectroscopy from a liquid microjet. Our measurements demonstrate unequivocally that metal-to-water charge transfer quenches fluorescence and will inevitably lead to a dip in the total-fluorescence-yield X-ray absorption spectrum. This is directly revealed from the resonant enhancement of valence signal intensity arising from the interference of two identical final states created by a direct and Auger-electron emission, respectively.

Shared solvation of sodium ions in alcohol-water solutions explains the non-ideality of free energy of solvation.

In order to explain the discrepancies between theories and experiments regarding the non-ideality in the free energy of solvation, here we present a microscopic picture of sodium ions dissolved in water-alcohol mixed solvents. We used X-ray absorption spectroscopy to probe the K-edge of sodium ions in mixed solvents of water and alcohols (methanol, ethanol) and in the respective pure solvents. In the mixed solvents a shared solvation of the sodium ions is observed. We find that specifically the water component plays a key role in stabilizing the solvation shell in mixed solvents, which was revealed by a selective photochemical process occurring only in the pure alcohol solvents.

Magnetic imaging at linearly polarized x-ray sources.

We present a method for high-resolution magnetic imaging at linearly polarized partially coherent x-ray sources. The magnetic imaging was realized via Fourier transform holography. In order to achieve elliptical x-ray polarization, three different filters were designed based on the x-ray magnetic circular dichroism effect. We present proof-of-principle images of magnetic nanostructures and discuss the application of the method for future experiments at free-electron laser sources.

Digital in-line holography with femtosecond VUV radiation provided by the free-electron laser FLASH.

Femtosecond vacuum ultraviolet (VUV) radiation provided by the free-electron laser FLASH was used for digital in-line holographic microscopy and applied to image particles, diatoms and critical point dried fibroblast cells. To realize the classical in-line Gabor geometry, a 1 microm pinhole was used as spatial filter to generate a divergent light cone with excellent pointing stability. At a fundamental wavelength of 8 nm test objects such as particles and diatoms were imaged at a spatial resolution of 620 nm. In order to demonstrate the applicability to biologically relevant systems, critical point dried rat embryonic fibroblast cells were for the first time imaged with free-electron laser radiation.

Holographic soft X-ray omni-microscopy of biological specimens.

Mask-based digital soft X-ray Fourier transform holography using coherent synchrotron radiation is applied to image diatoms and freeze-dried 3T3 fibroblast cells. At soft X-ray wavelengths between 4 nm and 8 nm we achieve spatial resolutions down to 450 nm over a 33.5 microm field of view. As holography records amplitude and phase of the scattered wavefield, images with different contrast mechanisms can be generated a posteriori by numerical processing of the holographic data ("omni-microscopy"). We present Zernike phase contrast, Schlieren phase contrast, differential interference and gradient contrast images based on amplitude and phase information. We discuss the potential of this approach for destructive single-shot imaging beyond dose limitations of biological samples at coherent femtosecond-pulsed X-ray sources.