Chemical Bonding in Aqueous Ferrocyanide: Experimental and Theoretical X‑ray Spectroscopic Study

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 σ-donation and π-backdonation. The effects are identified by comparing experimental and simulated spectra related to both the unoccupied and occupied molecular orbitals in solution

Transition-Metal Nanoparticle Oxidation in a Chemically Nonhomogenous Environment Revealed by 2p3d Resonant X‑ray Emission

X-ray absorption spectroscopy (XAS) is often employed in fields such as catalysis to determine whether transition-metal nanoparticles are oxidized. Here we show 2p_3/2XAS and 2p3d resonant X-ray emission spectroscopy (RXES) data of oleate-coated cobalt nanoparticles with average diameters of 4.0, 4.2, 5.0, 8.4, and 15.2 nm. Two particle batches were exposed to air for different periods of time, whereas the others were measured as synthesized. In the colloidal nanoparticles, the cobalt sites can have different chemical environments (metallic/oxidized/surface-coordinated), and it is shown that most XAS data cannot distinguish whether the nanoparticles are oxidized or surface-coated. In contrast, the high-energy resolution RXES spectra reveal whether more than the first metal layer is oxidized based on the unique energetic separation of spectral features related to the formal metal (X-ray fluorescence) or to a metal oxide (d-d excitations). This is the first demonstration of metal 2p3d RXES as a novel surface science tool