Synthesis, Structure, and Applications of Pyridiniophosphines

A new family of cationic ligands, N-alkyl/aryl pyridiniophosphines, has been synthesized through a short, scalable, and highly modular route. Evaluation of their electronic properties evidenced weak σ-donor and quite strong π-acceptor character when used as ancillary ligands. These attributes confer a substantially enhanced π-acidity to the PtII and AuI complexes thereof derived and, as result, they depict an improved ability to activate alkynes towards nucleophilic attack. This superior performance has been demonstrated along several mechanistically diverse PtII- and AuI-catalyzed transformations

Effect of dopants on thermal stability and self-diffusion in iron nitride thin films

We studied the effect of dopants (Al, Ti, Zr) on the thermal stability of iron nitride thin films prepared using a dc magnetron sputtering technique. Structure and magnetic characterization of deposited samples reveal that the thermal stability together with soft magnetic properties of iron nitride thin films get significantly improved with doping. To understand the observed results, detailed Fe and N self-diffusion measurements were performed. It was observed that N self-diffusion gets suppressed with Al doping whereas Ti or Zr doping results in somewhat faster N diffusion. On the other hand Fe self-diffusion seems to get suppressed with any dopant of which heat of nitride formation is significantly smaller than that of iron nitride. Importantly, it was observed that N self-diffusion plays only a trivial role, as compared to Fe self-diffusion, in affecting the thermal stability of iron nitride thin films. Based on the obtained results effect of dopants on self-diffusion process is discussed.Comment: 10 pages, 9 fig

Elucidating the structural composition of a Fe-N-C catalyst by nuclear and electron resonance techniques

Fe–N–C catalysts are very promising materials for fuel cells and metal–air batteries. This work gives fundamental insights into the structural composition of an Fe–N–C catalyst and highlights the importance of an in‐depth characterization. By nuclear‐ and electron‐resonance techniques, we are able to show that even after mild pyrolysis and acid leaching, the catalyst contains considerable fractions of α‐iron and, surprisingly, iron oxide. Our work makes it questionable to what extent FeN4 sites can be present in Fe–N–C catalysts prepared by pyrolysis at 900 °C and above. The simulation of the iron partial density of phonon states enables the identification of three FeN4 species in our catalyst, one of them comprising a sixfold coordination with end‐on bonded oxygen as one of the axial ligands

Intensity interferometry of single x-ray pulses from a synchrotron storage ring

We report on measurements of second-order intensity correlations at the high brilliance storage ring PETRA III using a prototype of the newly developed Adaptive Gain Integrating Pixel Detector (AGIPD). The detector recorded individual synchrotron radiation pulses with an x-ray photon energy of 14.4 keV and repetition rate of about 5 MHz. The second-order intensity correlation function was measured simultaneously at different spatial separations that allowed to determine the transverse coherence length at these x-ray energies. The measured values are in a good agreement with theoretical simulations based on the Gaussian Schell-model.Comment: 16 pages, 6 figures, 42 reference

Spin waves and spin-state transitions in a ruthenate high-temperature antiferromagnet

Ruthenium compounds play prominent roles in materials research ranging from oxide electronics to catalysis, and serve as a platform for fundamental concepts such as spin-triplet superconductivity, Kitaev spin-liquids, and solid-state analogues of the Higgs mode in particle physics. However, basic questions about the electronic structure of ruthenates remain unanswered, because several key parameters (including the Hund's-rule, spin-orbit, and exchange interactions) are comparable in magnitude, and their interplay is poorly understood - partly due to difficulties in synthesizing sizable single crystals for spectroscopic experiments. Here we introduce a resonant inelastic x-ray scattering (RIXS) technique capable of probing collective modes in microcrystals of $4d$-electron materials. We present a comprehensive set of data on spin waves and spin-state transitions in the honeycomb antiferromagnet SrRu$_{2}$O$_{6}$, which possesses an unusually high N\'eel temperature. The new RIXS method provides fresh insight into the unconventional magnetism of SrRu$_{2}$O$_{6}$, and enables momentum-resolved spectroscopy of a large class of $4d$ transition-metal compounds.Comment: The original submitted version of the published manuscript. https://www.nature.com/articles/s41563-019-0327-

Global Optimization by Energy Landscape Paving

We introduce a novel heuristic global optimization method, energy landscape paving (ELP), which combines core ideas from energy surface deformation and tabu search. In appropriate limits, ELP reduces to existing techniques. The approach is very general and flexible and is illustrated here on two protein folding problems. For these examples, the technique gives faster convergence to the global minimum than previous approaches.Comment: to appear in Phys. Rev. Lett. (2002

Interferometric phase detection at x-ray energies via Fano resonance control

Modern x-ray light sources promise access to structure and dynamics of matter in largely unexplored spectral regions. However, the desired information is encoded in the light intensity and phase, whereas detectors register only the intensity. This phase problem is ubiquitous in crystallography and imaging, and impedes the exploration of quantum effects at x-ray energies. Here, we demonstrate phase-sensitive measurements characterizing the quantum state of a nuclear two-level system at hard x-ray energies. The nuclei are initially prepared in a superposition state. Subsequently, the relative phase of this superposition is interferometrically reconstructed from the emitted x-rays. Our results form a first step towards x-ray quantum state tomography, and provide new avenues for structure determination and precision metrology via x-ray Fano interference.Comment: 5 pages, 3 figures, plus supplementary informatio

Tunable sub-luminal propagation of narrowband x-ray pulses

Group velocity control is demonstrated for x-ray photons of 14.4 keV energy via a direct measurement of the temporal delay imposed on spectrally narrow x-ray pulses. Sub-luminal light propagation is achieved by inducing a steep positive linear dispersion in the optical response of ${}^{57}$Fe M\"ossbauer nuclei embedded in a thin film planar x-ray cavity. The direct detection of the temporal pulse delay is enabled by generating frequency-tunable spectrally narrow x-ray pulses from broadband pulsed synchrotron radiation. Our theoretical model is in good agreement with the experimental data.Comment: 8 pages, 4 figure