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Author ORCID ID is 0000000272721603
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  1. A combined experimental and theoretical approach reveals correlations of metal L-edge X-ray absorption energies to local charge and spin densities.
  2. Transition metals in inorganic systems and metalloproteins can occur in different oxidation states, which makes them ideal redox-active catalysts. To gain a mechanistic understanding of the catalytic reactions, knowledge of the oxidation state of the active metals, ideally in operando, is therefore critical. L-edge X-ray absorption spectroscopy (XAS) is a powerful technique that is frequently used to infer the oxidation state via a distinct blue shift of L-edge absorption energies with increasing oxidation state. A unified description accounting for quantum-chemical notions whereupon oxidation does not occur locally on the metal but on the whole molecule and the basic understanding thatmore » L-edge XAS probes the electronic structure locally at the metal has been missing to date. We quantify how charge and spin densities change at the metal and throughout the molecule for both redox and core-excitation processes. We explain the origin of the L-edge XAS shift between the high-spin complexes Mn II(acac) 2 and Mn III(acac) 3 as representative model systems and use ab initio theory to uncouple effects of oxidation-state changes from geometric effects. The shift reflects an increased electron affinity of Mn III in the core-excited states compared to the ground state due to a contraction of the Mn 3d shell upon core-excitation with accompanied changes in the classical Coulomb interactions. This new picture quantifies how the metal-centered core hole probes changes in formal oxidation state and encloses and substantiates earlier explanations. The approach is broadly applicable to mechanistic studies of redox-catalytic reactions in molecular systems where charge and spin localization/delocalization determine reaction pathways.« less
  3. X-ray induced sample damage can impede electronic and structural investigations of radiation-sensitive samples studied with X-rays. Here we quantify dose-dependent sample damage to the prototypical Mn III(acac) 3 complex in solution and at room temperature for the soft X-ray range, using X-ray absorption spectroscopy at the Mn L-edge. We observe the appearance of a reduced Mn II species as the X-ray dose is increased. We find a half-damage dose of 1.6 MGy and quantify a spectroscopically tolerable dose on the order of 0.3 MGy (1 Gy = 1 J kg -1), where 90% of Mn III(acac) 3 are intact. Ourmore » dose-limit is around one order of magnitude lower than the Henderson limit (half-damage dose of 20 MGy) which is commonly employed for protein crystallography with hard X-rays. It is comparable, however, to the dose-limits obtained for collecting un-damaged Mn K-edge spectra of the photosystem II protein, using hard X-rays. The dose-dependent reduction of Mn III observed here for solution samples occurs at a dose limit that is two to four orders of magnitude smaller than the dose limits previously reported for soft X-ray spectroscopy of iron samples in the solid phase. We compare our measured to calculated spectra from ab initio restricted active space (RAS) theory and discuss possible mechanisms for the observed dose-dependent damage of Mn III(acac) 3 in solution. Lastly, on the basis of our results, we assess the influence of sample damage in other experimental studies with soft X-rays from storage-ring synchrotron radiation sources and X-ray free-electron lasers.« less
  4. Dose-dependent damage to a Mn iii complex in solution, induced by soft X-rays, is investigated with Mn L-edge X-ray absorption spectroscopy.
  5. X-ray crystallography at X-ray free-electron laser (XFEL) sources is a powerful method for studying macromolecules at biologically relevant temperatures. Moreover, when combined with complementary techniques like X-ray emission spectroscopy (XES), both global structures and chemical properties of metalloenzymes can be obtained concurrently, providing new insights into the interplay between the protein structure/dynamics and chemistry at an active site. However, implementing such a multimodal approach can be compromised by conflicting requirements to optimize each individual method. In particular, the method used for sample delivery greatly impacts the data quality. We present here a new, robust way of delivering controlled sample amountsmore » on demand using acoustic droplet ejection coupled with a conveyor belt drive that is optimized for crystallography and spectroscopy measurements of photochemical and chemical reactions over a wide range of time scales. Studies with photosystem II, the phytochrome photoreceptor, and ribonucleotide reductase R2 illustrate the power and versatility of this method.« less
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  6. The physics and chemistry of liquid solutions play a central role in science, and our understanding of life on Earth. Unfortunately, key tools for interrogating aqueous systems, such as infrared and soft X-ray spectroscopy, cannot readily be applied because of strong absorption in water. Here we use gas-dynamic forces to generate free-flowing, sub-micron, liquid sheets which are two orders of magnitude thinner than anything previously reported. Optical, infrared, and X-ray spectroscopies are used to characterize the sheets, which are found to be tunable in thickness from over 1 μm down to less than 20 nm, which corresponds to fewer thanmore » 100 water molecules thick. At this thickness, aqueous sheets can readily transmit photons across the spectrum, leading to potentially transformative applications in infrared, X-ray, electron spectroscopies and beyond. Lastly, the ultrathin sheets are stable for days in vacuum, and we demonstrate their use at free-electron laser and synchrotron light sources.« less

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