Magnesium is a key component used by many organisms in biomineralization. One role for magnesium is in stabilizing an otherwise unstable amorphous calcium carbonate (ACC) phase. The way in which this stabilization is achieved is unknown. Here, we address this question by studying the chemical environment around magnesium in biogenic and synthetic ACCs using Mg K-edge X-ray absorption spectroscopy (XAS). We show that although the short-range structure around the Mg ion is different in the various minerals studied, they all involve a shortening of the Mg−O bond length compared to crystalline anhydrous MgCO3 minerals. We propose that the compact structure around magnesium introduces distortion in the CaCO3 host mineral, thus inhibiting its crystallization. This study also shows that despite technical challenges in the soft X-ray energy regime, Mg K-edge XAS is a valuable tool for structural analysis of Mg containing amorphous materials, in biology and materials science.
We have studied enantiospecific differences in the adsorption of (S)- and (R)-alanine on Cu{531}
R
using
low-energy electron diffraction (LEED), X-ray photoelectron spectroscopy, and near edge X-ray absorption
fine structure (NEXAFS) spectroscopy. At saturation coverage, alanine adsorbs as alaninate forming a
p(1 × 4) superstructure. LEED shows a significantly higher degree of long-range order for the S than for the
R enantiomer. Also carbon K-edge NEXAFS spectra show differences between (S)- and (R)-alanine in the
variations of the π resonance when the linear polarization vector is rotated within the surface plane. This
indicates differences in the local adsorption geometries of the molecules, most likely caused by the interaction
between the methyl group and the metal surface and/or intermolecular hydrogen bonds. Comparison with
model calculations and additional information from LEED and photoelectron spectroscopy suggest that both
enantiomers of alaninate adsorb in two different orientations associated with triangular adsorption sites on
{110} and {311} microfacets of the Cu{531} surface. The experimental data are ambiguous as to the exact
difference between the local geometries of the two enantiomers. In one of two models that fit the data equally
well, significantly more (R)-alaninate molecules are adsorbed on {110} sites than on {311} sites whereas for
(S)-alaninate the numbers are equal. The enantiospecific differences found in these experiments are much
more pronounced than those reported from other ultrahigh vacuum techniques applied to similar systems.
Tweaking the properties of carbon nanotubes is a prerequisite for their practical applications.Here we demonstrate fine-tuning the electronic properties of single-wall carbon nanotubes via filling with ferrocene molecules. The evolution of the bonding and charge transfer within the tube is demonstrated via chemical reaction of the ferrocene filler ending up as secondary inner tube. The charge transfer nature is interpreted well within density functional theory. This work gives the first direct observation of a fine-tuned continuous amphoteric doping of single-wall carbon nanotubes.
The excitement of nano-test-tube chemistry in a single-walled carbon nanotube is exemplified in our study on electron doping in carbon nanotubes. Electron doping through the 1D van Hove singularity of single-walled carbon nanotubes is realized via a chemical reaction of an encapsulated organocerium compound, CeCp 3 . The decomposition of CeCp 3 inside the carbon nanotubes increases the doping level and greatly enhances the density of conduction electrons. The transition of the cerium encapsulating semiconducting tubes to metallic results in enhanced screening of the photoexcited core hole potential. This fact illustrates the importance of many body effects in understanding core-level excitation process in carbon nanotubes.
We present a high-resolution photoelectron spectroscopy investigation of condensed films of benzene, naphthalene, anthracene, tetracene, and pentacene. High spectroscopic resolution and a systematic variation of the molecular size allow a detailed analysis of the fine structures. The line shapes of the C 1s main lines are analyzed with respect to the different contributions of inhomogeneous broadening, vibronic coupling, and chemical shifts. The shake-up satellite spectra reveal trends, which give insight into the charge redistribution within the molecule upon photoexcitation. In particular, the shake-up between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) increases in intensity and moves closer toward the C 1s main line if the size of the aromatic system is increased. An explanation is given on the basis of the delocalization of the aromatic system and its capability in screening the photogenerated core hole. A comparison of the HOMO-LUMO shake-up position to the optical band gap gives additional insight into the reorganization of the electronic system upon photoexcitation.
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