Charge-Transfer Analysis of 2p3d Resonant Inelastic X-ray Scattering of Cobalt Sulfide and Halides.
ABSTRACT: We show that with 2p3d resonant inelastic X-ray scattering (RIXS) we can accurately determine the charge-transfer parameters of CoF2, CoCl2, CoBr2, and CoS. The 160 meV resolution RIXS results are compared with charge-transfer multiplet calculations. The improved resolution and the direct observation of the crystal field and charge-transfer excitations allow the determination of more accurate parameters than could be derived from X-ray absorption and X-ray photoemission, both limited in resolution by their lifetime broadening. We derive the crystal field and charge-transfer parameters of the Co2+ ions, which provides the nature of the ground state of the Co2+ ions with respect to symmetry and hybridization. In addition, the increased spectral resolution allows the more accurate determination of the atomic Slater integrals. The results show that the crystal field energy decreases with increasing ligand covalency. The L2 edge RIXS spectra show that the intensity of the (Coster-Kronig induced) nonresonant X-ray emission is a measure of ligand covalency.
Project description:The role of transition metals in chemical reactions is often derived from probing the metal 3d states. However, the relation between metal site geometry and 3d electronic states, arising from multielectronic effects, makes the spectral data interpretation and modeling of these optical excited states a challenge. Here we show, using the well-known case of red ruby, that unique insights into the density of transition metal 3d excited states can be gained with 2p3d resonant inelastic X-ray scattering (RIXS). We compare the experimental determination of the 3d excited states of Cr3+ impurities in Al2O3 with 190 meV resolution 2p3d RIXS to optical absorption spectroscopy and to simulations. Using the crystal field multiplet theory, we calculate jointly for the first time the Cr3+ multielectronic states, RIXS, and optical spectra based on a unique set of parameters. We demonstrate that (i) anisotropic 3d multielectronic interactions causes different scaling of Slater integrals, and (ii) a previously not observed doublet excited state exists around 3.35 eV. These results allow to discuss the influence of interferences in the RIXS intermediate state, of core-hole lifetime broadenings, and of selection rules on the RIXS intensities. Finally, our results demonstrate that using an intermediate excitation energy between L3 and L2 edges allows measurement of the density of 3d excited states as a fingerprint of the metal local structure. This opens up a new direction to pump-before-destroy investigations of transition metal complex structures and reaction mechanisms.
Project description:Data from K? resonant inelastic X-ray scattering (RIXS) have been used to extract electronic structure information, i.e., the covalency of metal-ligand bonds, for four iron complexes using an experimentally based theoretical model. K? RIXS involves resonant 1s?3d excitation and detection of the 2p?1s (K?) emission. This two-photon process reaches similar final states as single-photon L-edge (2p?3d) X-ray absorption spectroscopy (XAS), but involves only hard X-rays and can therefore be used to get high-resolution L-edge-like spectra for metal proteins, solution catalysts and their intermediates. To analyze the information content of K? RIXS spectra, data have been collected for four characteristic ?-donor and ?-back-donation complexes: ferrous tacn [Fe(II)(tacn)2]Br2, ferrocyanide [Fe(II)(CN)6]K4, ferric tacn [Fe(III)(tacn)2]Br3 and ferricyanide [Fe(III)(CN)6]K3. From these spectra metal-ligand covalencies can be extracted using a charge-transfer multiplet model, without previous information from the L-edge XAS experiment. A direct comparison of L-edge XAS and K? RIXS spectra show that the latter reaches additional final states, e.g., when exciting into the e(g) (?*) orbitals, and the splitting between final states of different symmetry provides an extra dimension that makes K? RIXS a more sensitive probe of ?-bonding. Another key difference between L-edge XAS and K? RIXS is the ?-back-bonding features in ferro- and ferricyanide that are significantly more intense in L-edge XAS compared to K? RIXS. This shows that two methods are complementary in assigning electronic structure. The K? RIXS approach can thus be used as a stand-alone method, in combination with L-edge XAS for strongly covalent systems that are difficult to probe by UV/vis spectroscopy, or as an extension to conventional absorption spectroscopy for a wide range of transition metal enzymes and catalysts.
Project description:Photoinduced intramolecular electron transfer dynamics following metal-to-ligand charge-transfer (MLCT) excitation of [Fe(CN)<sub>4</sub>(2,2'-bipyridine)]<sup>2-</sup> (<b>1</b>), [Fe(CN)<sub>4</sub>(2,3-bis(2-pyridyl)pyrazine)]<sup>2-</sup> (<b>2</b>) and [Fe(CN)<sub>4</sub>(2,2'-bipyrimidine)]<sup>2-</sup> (<b>3</b>) were investigated in various solvents with static and time-resolved UV-Visible absorption spectroscopy and Fe 2p3d resonant inelastic X-ray scattering (RIXS). This series of polypyridyl ligands, combined with the strong solvatochromism of the complexes, enables the <sup>1</sup>MLCT vertical energy to be varied from 1.64 eV to 2.64 eV and the <sup>3</sup>MLCT lifetime to range from 180 fs to 67 ps. The <sup>3</sup>MLCT lifetimes in <b>1</b> and <b>2</b> decrease exponentially as the MLCT energy increases, consistent with electron transfer to the lowest energy triplet metal-centred (<sup>3</sup>MC) excited state, as established by the Tanabe-Sugano analysis of the Fe 2p3d RIXS data. In contrast, the <sup>3</sup>MLCT lifetime in <b>3</b> changes non-monotonically with MLCT energy, exhibiting a maximum. This qualitatively distinct behaviour results from a competing <sup>3</sup>MLCT → ground state (GS) electron transfer pathway that exhibits energy gap law behaviour. The <sup>3</sup>MLCT → GS pathway involves nuclear tunnelling for the high-frequency polypyridyl breathing mode (<i>hν</i> = 1530 cm<sup>-1</sup>), which is most displaced for complex <b>3</b>, making this pathway significantly more efficient. Our study demonstrates that the excited state relaxation mechanism of Fe polypyridyl photosensitizers can be readily tuned by ligand and solvent environment. Furthermore, our study reveals that extending charge transfer lifetimes requires control of the relative energies of the <sup>3</sup>MLCT and the <sup>3</sup>MC states and suppression of the intramolecular distortion of the acceptor ligand in the <sup>3</sup>MLCT excited state.
Project description:In-situ carbon-thermal reduction of cobalt oxide nanoparticles supported on carbon nanotubes was studied by cobalt 2p3d resonant inelastic X-ray scattering (RIXS). The in-situ 2p X-ray absorption spectroscopy (XAS) and RIXS measurements were performed at 500, 600, and 700 °C, where four consistent excitation energies were used for RIXS acquisitions. After 700 °C reduction, the XAS spectrum shows a cobalt metal-like shape, while the RIXS spectra reveal the minority cobalt monoxide phase. The holistic fit on both XAS and RIXS data reveals the respective contributions from metal and monoxide. We show that the relative precision to determine the monoxide content changes from ?5.6% in XAS results to better than 0.8% in the RIXS analysis, suggesting that RIXS is a useful tool to track the oxidation state of nanoparticles under in situ conditions. We determined a relative radiative ratio (P) factor of approximately 5, where this factor gives the ratio between the relative strengths of the radiative decay channels compared to the nonradiative channels in CoO and Co metal.
Project description:Secondary batteries are important energy storage devices for a mobile equipment, an electric car, and a large-scale energy storage. Nevertheless, variation of the local electronic state of the battery materials in the charge (or oxidization) process are still unclear. Here, we investigated the local electronic state of cobalt-hexacyanoferrate (Na x Co[Fe(CN)6]0.9), by means of resonant inelastic X-ray scattering (RIXS) with high energy resolution (~100?meV). The L-edge RIXS is one of the most powerful spectroscopic technique with element- and valence-selectivity. We found that the local electronic state around Co2+ in the partially-charged Na1.1Co2+0.5Co3+0.5[Fe2+(CN)6]0.9 film (x?=?1.1) is the same as that of the discharged Na1.6Co2+[Fe2+(CN)6]0.9 film (x?=?1.6) within the energy resolution, indicating that the local electronic state around Co2+ is invariant against the partial oxidization. In addition, the local electronic state around the oxidized Co3+ is essentially the same as that of the fully-charged film Co3+[Fe2+(CN)6]0.3[Fe3+(CN)6]0.6 (x?=?0.0) film. Such a strong localization of the oxidized Co3+ state is advantageous for the reversibility of the redox process, since the localization reduces extra reaction within the materials and resultant deterioration.
Project description:Axial Cu-S(Met) bonds in electron transfer (ET) active sites are generally found to lower their reduction potentials. An axial S(Met) bond is also present in cytochrome c (cyt c) and is generally thought to increase the reduction potential. The highly covalent nature of the porphyrin environment in heme proteins precludes using many spectroscopic approaches to directly study the Fe site to experimentally quantify this bond. Alternatively, L-edge X-ray absorption spectroscopy (XAS) enables one to directly focus on the 3d-orbitals in a highly covalent environment and has previously been successfully applied to porphyrin model complexes. However, this technique cannot be extended to metalloproteins in solution. Here, we use metal K-edge XAS to obtain L-edge like data through 1s2p resonance inelastic X-ray scattering (RIXS). It has been applied here to a bis-imidazole porphyrin model complex and cyt c. The RIXS data on the model complex are directly correlated to L-edge XAS data to develop the complementary nature of these two spectroscopic methods. Comparison between the bis-imidazole model complex and cyt c in ferrous and ferric oxidation states show quantitative differences that reflect differences in axial ligand covalency. The data reveal an increased covalency for the S(Met) relative to N(His) axial ligand and a higher degree of covalency for the ferric states relative to the ferrous states. These results are reproduced by DFT calculations, which are used to evaluate the thermodynamics of the Fe-S(Met) bond and its dependence on redox state. These results provide insight into a number of previous chemical and physical results on cyt c.
Project description:Ru-complexes are widely studied because of their use in biological applications and photoconversion technologies. We reveal novel insights into the chemical bonding of a series of Ru(ii)- and Ru(iii)-complexes by leveraging recent advances in high-energy-resolution tender X-ray spectroscopy and theoretical calculations. We perform Ru 2p4d resonant inelastic X-ray scattering (RIXS) to probe the valence excitations in dilute solvated Ru-complexes. Combining these experiments with a newly developed theoretical approach based on time-dependent density functional theory, we assign the spectral features and quantify the metal-ligand bonding interactions. The valence-to-core RIXS features uniquely identify the metal-centered and charge transfer states and allow extracting the ligand-field splitting for all the complexes. The combined experimental and theoretical approach described here is shown to reliably characterize the ground and excited valence states of Ru complexes, and serve as a basis for future investigations of ruthenium, or other 4d metals active sites, in biological and chemical applications.
Project description:The metal-insulator transition and the intriguing physical properties of rare-earth perovskite nickelates have attracted considerable attention in recent years. Nonetheless, a complete understanding of these materials remains elusive. Here we combine X-ray absorption and resonant inelastic X-ray scattering (RIXS) spectroscopies to resolve important aspects of the complex electronic structure of rare-earth nickelates, taking NdNiO<sub>3</sub> thin film as representative example. The unusual coexistence of bound and continuum excitations observed in the RIXS spectra provides strong evidence for abundant oxygen holes in the ground state of these materials. Using cluster calculations and Anderson impurity model interpretation, we show that distinct spectral signatures arise from a Ni 3d<sup>8</sup> configuration along with holes in the oxygen 2p valence band, confirming suggestions that these materials do not obey a conventional positive charge-transfer picture, but instead exhibit a negative charge-transfer energy in line with recent models interpreting the metal-insulator transition in terms of bond disproportionation.
Project description:We demonstrate for the case of photoexcited [Ru(2,2'-bipyridine)<sub>3</sub>]<sup>2+</sup> how femtosecond resonant inelastic X-ray scattering (RIXS) at the ligand K-edge allows one to uniquely probe changes in the valence electronic structure following a metal-to-ligand charge-transfer (MLCT) excitation. Metal-ligand hybridization is probed by nitrogen-1s resonances providing information on both the electron-accepting ligand in the MLCT state and the hole density of the metal center. By comparing to spectrum calculations based on density functional theory, we are able to distinguish the electronic structure of the electron-accepting ligand and the other ligands and determine a temporal upper limit of (250 ± 40) fs for electron localization following the charge-transfer excitation. The spin of the localized electron is deduced from the selection rules of the RIXS process establishing new experimental capabilities for probing transient charge and spin densities.
Project description:Continued improvement of the energy resolution of resonant inelastic x-ray scattering (RIXS) spectrometers is crucial for fulfilling the potential of this technique in the study of electron dynamics in materials of fundamental and technological importance. In particular, RIXS is the only alternative tool to inelastic neutron scattering capable of providing fully momentum resolved information on dynamic spin structures of magnetic materials, but is limited to systems whose magnetic excitation energy scales are comparable to the energy resolution. The state-of-the-art spherical diced crystal analyzer optics provides energy resolution as good as 25 meV but has already reached its theoretical limit. Here, we demonstrate a novel sub-10 meV RIXS spectrometer based on flat-crystal optics at the Ir-L3 absorption edge (11.215 keV) that achieves an analyzer energy resolution of 3.9 meV, very close to the theoretical value of 3.7 meV. In addition, the new spectrometer allows efficient polarization analysis without loss of energy resolution. The performance of the instrument is demonstrated using longitudinal acoustical and optical phonons in diamond, and magnon in Sr3Ir2O7. The novel sub-10 meV RIXS spectrometer thus provides a window into magnetic materials with small energy scales.