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In this work, we investigate the photo-aquation reaction of the ferrocyanide anion with multi-edge picosecond soft X-ray spectroscopy. Combining the information of the iron L-edge with nitrogen and oxygen K-edges, we carry out a complete characterization of the bonding channels in the [Fe(CN)(5)(H2O)](3-) photo-product. We observe clear spectral signatures of covalent bonding between water and the metal, reflecting the mixing of the Fe d(z)(2) orbital with the 3a(1) and 4a(1) orbitals of H2O. Additional fingerprints related to the symmetry reduction and the resulting loss in orbital degeneracy are also reported. The implications of the elucidated fingerprints in the context of future ultra-fast experiments are also discussed.

Manganese–oxo species catalyze key reactions, including C–H bond activation or dioxygen formation in natural photosynthesis. To better understand relevant reaction intermediates, we characterize electronic states and geometric structures of [MnOn]+ manganese–oxo complexes that represent a wide range of manganese oxidation states. To this end, we apply soft X-ray spectroscopy in a cryogenic ion trap, combined with multiconfigurational wavefunction calculations. We identify [MnO2]+ as a rare high-spin manganese(V) oxo complex with key similarities to six-coordinated manganese(V) oxo systems that are proposed as reaction intermediates in catalytic dioxygen bond formation.

The fluctuating hydrogen bridge bonded network of liquid water at ambient conditions entails a varied ensemble of the underlying constituting H 2 O molecular moieties. This is mirrored in a manifold of the H 2 O molecular potentials. Subnatural line width resonant inelastic X-ray scattering allowed us to quantify the manifold of molecular potential energy surfaces along the H 2 O symmetric normal mode and the local asymmetric O–H bond coordinate up to 1 and 1.5 Å, respectively. The comparison of the single H 2 O molecular potentials and spectroscopic signatures with the ambient conditions liquid phase H 2 O molecular potentials is done on various levels. In the gas phase, first principles, Morse potentials, and stepwise harmonic potential reconstruction have been employed and benchmarked. In the liquid phase the determination of the potential energy manifold along the local asymmetric O–H bond coordinate from resonant inelastic X-ray scattering via the bound state oxygen 1 s to 4 a 1 resonance is treated within these frameworks. The potential energy surface manifold along the symmetric stretch from resonant inelastic X-ray scattering via the oxygen 1 s to 2 b 2 resonance is based on stepwise harmonic reconstruction. We find in liquid water at ambient conditions H 2 O molecular potentials ranging from the weak interaction limit to strongly distorted potentials which are put into perspective to established parameters, i.e., intermolecular O–H, H–H, and O–O correlation lengths from neutron scattering.

A stable salt of the metalloradical [Ni C6H6 2] hitherto unknown in the condensed phase was synthesized from [Ni CO 4] [WCA] amp; 8722; and benzene [WCA] amp; 8722; [F Al ORF 3 2] amp; 8722;; RF C CF3 3 . Single crystal XRD reveals a remarkable asymmetrically amp; 951;3, amp; 951;6 slipped sandwich structure. The magnetic properties of the [Ni C6H6 2] cation were determined in solution and in the gas phase. Oxidation with the synergistic Ag 0.5 amp; 8197;l2 system led to the salt [Ni C6H6 2]2 [WCA] amp; 8722; 2. All products were fully characterized by means of IR, Raman, NMR EPR, single crystal and powder XRD

Auger photoelectron coincidence spectroscopy APECS has been used to examine the electron correlation and itinerance effects in transition metals Cu, Ni and Co. It is shown that the LVV Auger, in coincidence with 2p photoelectrons, spectra can be represented using atomic multiplet positions if the 3d shell is localized atomic like and with a self convoluted valence band for band like itinerant materials as explained using the Cini Sawatzky model. For transition metals, the 3d band changes from band like to localized with increasing atomic number, with the possibility of a mixed behavior. Our result shows that the LVV spectra of Cu can be represented by atomic multiplet calculations, those of Co resemble the self convolution of the valence band and those of Ni are a mixture of both, consistent with the Cini Sawatzky model

International audience; We characterize experimentally and theoretically the high-energy dielectric screening properties of the prototypical correlated metal SrVO$_3$. The dynamical structure factor measured by inelastic x-ray scattering spectroscopy as a function of momentum transfer is in very good agreement with first-principles calculations in the adiabatic local density approximation to time-dependent density-functional theory. Our results reveal the crucial importance of crystal local fields in the charge response function of correlated materials: They lead to depolarization effects for localised excitations and couple spectra from different Brillouin zones.

Physical chemistry, chemical physics 23(14), 8246 - 8260 (2021). doi:10.1039/D1CP00430A, We report on the effects of electron collision and indirect ionization processes, occurring at photoexcitation and electron kinetic energies well below 30 eV, on the photoemission spectra of liquid water. We show that the nascent photoelectron spectrum and, hence, the inferred electron binding energy can only be accurately determined if electron energies are large enough that cross sections for quasi-elastic scattering processes, such as vibrational excitation, are negligible. Otherwise, quasi-elastic scattering leads to strong, down-to-few-meV kinetic energy scattering losses from the direct photoelectron features, which manifest in severely distorted intrinsic photoelectron peak shapes. The associated cross-over point from predominant (known) electronically inelastic to quasi-elastic scattering seems to arise at surprisingly large electron kinetic energies, of approximately 10–14 eV. Concomitantly, we present evidence for the onset of indirect, autoionization phenomena (occurring via superexcited states) within a few eV of the primary and secondary ionization thresholds. These processes are inferred to compete with the direct ionization channels and primarily produce low-energy photoelectrons at photon and electron impact excitation energies below ∼15 eV. Our results highlight that vibrational inelastic electron scattering processes and neutral photoexcitation and autoionization channels become increasingly important when photon and electron kinetic energies are decreased towards the ionization threshold. Correspondingly, we show that for neat water and aqueous solutions, great care must be taken when quantitatively analyzing photoelectron spectra measured too close to the ionization threshold. Such care is essential for the accurate determination of solvent and solute ionization energies as well as photoelectron branching ratios and peak magnitudes., Published by RSC Publ., Cambridge

Scientific reports 11(1), 1883 (2021). doi:10.1038/s41598-021-81177-9, How different microscopic mechanisms of ultrafast spin dynamics coexist and interplay is not only relevant for the development of spintronics but also for the thorough description of physical systems out-of-equilibrium. In pure crystalline ferromagnets, one of the main microscopic mechanism of spin relaxation is the electron-phonon (el-ph) driven spin-flip, or Elliott-Yafet, scattering. Unexpectedly, recent experiments with ferro- and ferrimagnetic alloys have shown different dynamics for the different sublattices. These distinct sublattice dynamics are contradictory to the Elliott-Yafet scenario. In order to rationalize this discrepancy, it has been proposed that the intra- and intersublattice exchange interaction energies must be considered in the microscopic demagnetization mechanism, too. Here, using a temperature-dependent x-ray emission spectroscopy (XES) method, we address experimentally the element specific el-ph angular momentum transfer rates, responsible for the spin-flips in the respective (sub)lattices of Fe20Ni80, Fe50Ni50 and pure nickel single crystals. We establish how the deduced rate evolution with the temperature is linked to the exchange coupling constants reported for different alloy stoichiometries and how sublattice exchange energies threshold the related el-ph spin-flip channels. Thus, these results evidence that the Elliott-Yafet spin-flip scattering, thresholded by sublattice exchange energies, is the relevant microscopic process to describe sublattice dynamics in alloys and elemental magnetic systems., Published by Macmillan Publishers Limited, part of Springer Nature, [London]

Physical review / A 104(1), 013114 (2021). doi:10.1103/PhysRevA.104.013114, We study theoretically x-ray absorption and ionization spectra of an atom or molecule by two coherent x-ray pulses that show a relative phase shift resulting in a time delay of the pulse envelopes. We demonstrate that the phase modulation of the spectra is shifted with respect to the phase oscillation comb of the x-ray double pulse. The reason for this shift is the dynamics of the process defined by the interplay of the delay time, the pulse width, the detuning, and the lifetime of the core-excited state., Published by Inst., Woodbury, NY

In article number 2006957, Nomi L. A. N. Sorgenfrei and co workers demonstrate that a weak optical excitation creates electrons in the conduction band of p doped semiconducting molybdenum disulfide, which travel toward the surface layer. They accumulate in the top layer and concomitantly drive it from the semiconducting toward the metallic phase. The selectivity of synchrotron time resolved electron spectroscopy traces this effect. This surface modification influences the properties and functionality of MoS2. Frontispiece Art Martin Künsting

The extension of the pump-probe approach known from UV/VIS spectroscopy to very short wavelengths together with advanced simulation techniques allows a detailed analysis of excited-state dynamics in organic molecules or biomolecular structures on a nanosecond to femtosecond time level. Optical pump soft X-ray probe spectroscopy is a relatively new approach to detect and characterize optically dark states in organic molecules, exciton dynamics or transient ligand-to-metal charge transfer states. In this paper, we describe two experimental setups for transient soft X-ray absorption spectroscopy based on an LPP emitting picosecond and sub-nanosecond soft X-ray pulses in the photon energy range between 50 and 1500 eV. We apply these setups for near-edge X-ray absorption fine structure (NEXAFS) investigations of thin films of a metal-free porphyrin, an aggregate forming carbocyanine and a nickel oxide molecule. NEXAFS investigations have been carried out at the carbon, nitrogen and oxygen K-edge as well as on the Ni L-edge. From time-resolved NEXAFS carbon, K-edge measurements of the metal-free porphyrin first insights into a long-lived trap state are gained. Our findings are discussed and compared with density functional theory calculations.