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Register a new userChemical Bonding in Aqueous Ferrocyanide: Experimental and Theoretical X-ray Spectroscopic Study
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Resonant inelastic X-ray scattering (RIXS) and X-ray absorption (XA) experiments at the iron L- and nitrogen K-edge are combined with high-level first principles restricted active space self-consistent field (RASSCF) calculations for a systematic investigation of the nature of the chemical bond in potassium ferrocyanide in aqueous solution. The atom- and site-specific RIXS excitations allow for direct observation of ligand-to-metal (Fe L-edge) and metal-to-ligand (N K-edge) charge transfer bands and thereby evidence for strong {sigma}-donation and {pi}-back-donation. The effects are identified by comparing experimental and simulated spectra related to both the unoccupied and occupied molecular orbitals in solution.
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The search and exploration of new materials not found in nature is one of modern trends in pure and applied chemistry. In the present work, we report on experimental and textit{ab initio} density-functional study of the high-pressure-synthesized series of compounds Mn$_{1-x}$(Co,Rh)$_x$Ge. These high-pressure phases remain metastable at normal conditions, therewith they preserve their inherent noncentrosymmetric B20-type structure and chiral magnetism. Of particular interest in these two isovalent systems is the comparative analysis of the effect of $3d$ (Co) and $4d$ (Rh) substitution for Mn, since the $3d$ orbitals are characterized by higher localization and electron interaction than the $4d$ orbitals. The behavior of Mn$_{1-x}$(Co,Rh)$_x$Ge systems is traced as the concentration changes in the range $0 leq x leq 1$. We applied a sensitive experimental and theoretical technique which allowed to refine the shape of the temperature dependencies of magnetic susceptibility $chi(T)$ and thereby provide a new and detailed magnetic phase diagram of Mn$_{1-x}$Co$_x$Ge. It is shown that both systems exhibit a helical magnetic ordering that very strongly depends on the composition $x$. However, the phase diagram of Mn$_{1-x}$Co$_x$Ge differs from that of Mn$_{1-x}$Rh$_x$Ge in that it is characterized by coexistence of two helices in particular regions of concentrations and temperatures.
Due to its exceptional lithium storage capacity silicon is considered as a promising candidate for anode material in lithium-ion batteries (LIBs). In the present work we demonstrate that methods of the soft X-ray emission spectroscopy (SXES) can be used as a powerful tool for the comprehensive analysis of the electronic and structural properties of lithium silicides Li$_{x}$Si forming in LIBs anode upon Si lithiation. On the basis of density functional theory (DFT) and molecular dynamics (MD) simulations it is shown that coordination of Si atoms in Li$_{x}$Si decreases with increase in Li concentration both for the crystalline and amorphous phases. In amorphous a-Li$_{x}$Si alloys Si tends to cluster forming Si-Si covalent bonds even at the high lithium concentration. It is demonstrated that the Si-L$_{2,3}$ emission bands of the crystalline and amorphous Li$_{x}$Si alloys show different spectral dependencies reflecting the process of disintegration of Si-Si network into Si clusters and chains of the different sizes upon Si lithiation. The Si-L$_{2,3}$ emission band of Li$_{x}$Si alloys become narrower and shifts towards higher energies with an increase in Li concentration. The shape of the emission band depends on the relative contribution of the X-ray radiation from the Si atoms having different coordination. This feature of the Si-L$_{2,3}$ spectra of Li$_{x}$Si alloys can be used for the detailed analysis of the Si lithiation process and LIBs anode structure identification.
The performance of gold nanoparticles (NPs) in applications depends critically on the structure of the NP-solvent interface, at which the electrostatic surface polarization is one of the key characteristics that affects hydration, ionic adsorption, and electrochemical reactions. Here, we demonstrate significant effects of explicit metal polarizability on the solvation and electrostatic properties of bare gold NPs in aqueous electrolyte solutions of sodium salts of various anions (Cl$^-$, BF$_4$$^-$, PF$_6$$^-$, Nip$^-$(nitrophenolate), and 3- and 4-valent hexacyanoferrate (HCF)), using classical molecular dynamics simulations with a polarizable core-shell model of the gold atoms. We find considerable spatial heterogeneity of the polarization and electrostatic potentials on the NP surface, mediated by a highly facet-dependent structuring of the interfacial water molecules. Moreover, ion-specific, facet-dependent ion adsorption leads to large alterations of the interfacial polarization. Compared to non-polarizable NPs, polarizability modifies water local dipole densities only slightly, but has substantial effects on the electrostatic surface potentials, and leads to significant lateral redistributions of ions on the NP surface. Besides, interfacial polarization effects on the individual monovalent ions cancel out in the far field, and effective Debye-Huckel surface potentials remain essentially unaffected, as anticipated from continuum `image-charge concepts. Hence, the explicit charge response of metal NPs is crucial for the accurate description and interpretation of interfacial electrostatics (as, e.g., for charge transfer and interface polarization in catalysis and electrochemistry).
Irradiation with high energy photons (10.2 - 11.8 eV) was applied to small diamondoids isolated in solid rare gas matrices at low temperature. The photoproducts were traced via UV absorption spectroscopy. We found that upon ionization the smallest of these species lose a peripheral H atom to form a stable closed-shell cation. This process is also likely to occur under astrophysical conditions for gas phase diamondoids and it opens the possibility to detect diamond-like molecules using their rotational spectrum since the dehydrogenated cations possess strong permanent dipole moments. The lowest-energy electronic features of these species in the UV were found to be rather broad, shifting to longer wavelengths with increasing molecular size. Calculations using time-dependent density functional theory support our experimental findings and extend the absorption curves further into the vacuum ultraviolet. The complete sigma - sigma* spectrum displays surprisingly strong similarities to meteoritic nanodiamonds containing 50 times more C atoms.
The electronic structure of the nanolaminated transition metal carbide Ti2AlC has been investigated by bulk-sensitive soft x-ray emission spectroscopy. The measured Ti L, C K and Al L emission spectra are compared with calculated spectra using ab initio density-functional theory including dipole matrix elements. The detailed investigation of the electronic structure and chemical bonding provides increased understanding of the physical properties of this type of nanolaminates. Three different types of bond regions are identified; the relatively weak Ti 3d - Al 3p hybridization 1 eV below the Fermi level, and the Ti 3d - C 2p and Ti 3d - C 2s hybridizations which are stronger and deeper in energy are observed around 2.5 eV and 10 eV below the Fermi level, respectively. A strongly modified spectral shape of the 3s final states in comparison to pure Al is detected for the buried Al monolayers indirectly reflecting the Ti 3d - Al 3p hybridization. The differences between the electronic and crystal structures of Ti2AlC, Ti3AlC2 and TiC are discussed in relation to the number of Al layers per Ti layer in the two former systems and the corresponding change of the unusual materials properties.
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