Ewelina Magos-Palasyuk

Bio: Ewelina Magos-Palasyuk is an academic researcher from Polish Academy of Sciences. The author has contributed to research in topics: Hydrogen bond & Ammonia borane. The author has an hindex of 4, co-authored 6 publications receiving 3665 citations.

Ammonia as a case study for the spontaneous ionization of a simple hydrogen-bonded compound

Abstract: Ionization of highly compressed ammonia has previously been predicted by computation. Here, the authors provide experimental evidence for this autoionization process at high pressures, showing the transformation of molecular ammonia into ammonium amide.

M(BH3NH2BH2NH2BH3)--the missing link in the mechanism of the thermal decomposition of light alkali metal amidoboranes.

Abstract: We report a novel family of hydrogen-rich materials – alkali metal di(amidoborane)borohydrides, M(BH3NH2BH2NH2BH3). The title compounds are related to metal amidoboranes (amidotrihydroborates) but have higher gravimetric H content. Li salt contains 15.1 wt% H and discharges very pure H2 gas. Differences in thermal stability between amidoboranes and respective oligoamidoboranes explain the release of the ammonia impurity (along with H2) during the thermal decomposition of light alkali amidoboranes, LiNH2BH3, NaNH2BH3 and NaLi(NH2BH3)2, and confirm the mechanism of the side decomposition reaction.

Chemically driven negative linear compressibility in sodium amidoborane, Na(NH2BH3).

Abstract: Over the past few years we have been witnessing a surge of scientific interest to materials exhibiting a rare mechanical effect such as negative linear compressibility (NLC). Here we report on strong NLC found in an ionic molecular crystal of sodium amidoborane (NaAB) – easily-accessible, optically transparent material. In situ Raman measurements revealed abnormal elongation of B-N and N-H bonds of NaAB at pressure about 3 GPa. Ab initio calculations indicate the observed spectroscopic changes are due to an isostructural phase transition accompanied by a stepwise expansion of the crystal along c axis. Analysis of calculated charge density distribution and geometry of molecular species (NH2BH3) univocally points to a chemically driven mechanism of NLC – pressure-induced formation of hydrogen bonds. The new H-bond acts as a “pivot screw” coupling N-H covalent bonds of neighbor molecular species – a system resembling a two-lever “jack device” on a molecular scale. A mechanism based on formation of new bonds stands in apparent contrast to mechanisms so far reported in majority of NLC materials where no significant alteration of chemical bonding was observed. The finding therefore suggests a qualitatively new direction in exploration the field towards rational design of incompressible materials.

Hydrogen-mediated affinity of ions found in compressed potassium amidoborane, K[NH2BH3]

Abstract: The paper reports on the experimental and theoretical investigation of bonding properties of potassium amidoborane, (K[NH2BH3]), which is one of the most promising compounds for hydrogen storage material among metallated derivatives of ammonia borane (NH3BH3). For this purpose, in situ Raman spectroscopy, synchrotron X-ray diffraction measurements and complementary ab initio calculations study have been performed under static pressure conditions in the range from ambient pressure up to 25 GPa. Unusual interplay between strong electrostatic and weak dispersive interactions has been revealed, resulting in experimental observation of pressure induced formation of relatively strong conventional hydrogen bonding between negatively charged molecular ions. This finding provides new insight for tailoring materials with desirable properties for various uses.

Experimental and theoretical evidence of dihydrogen bonds in lithium amidoborane.

Abstract: In situ high-pressure synchrotron X-ray diffraction, Raman scattering, and complementary first-principles calculations have revealed that structural and spectroscopic properties of lithium amidoborane compound are largely determined by multiple heteropolar dihydrogen bonds. The crystal structure of the compound is stabilized by dimeric complexes, wherein molecular ions bind together by intermolecular dihydrogen bonds of unconventional type. This strong intermolecular coupling determines stable character of the crystal structure in the pressure range up to ~ 30 GPa and is spectroscopically manifested by pronounced changes related to molecular vibrations of the amino group: the splitting of stretching modes, the anomalous behavior of wagging modes as well as Fermi resonance due to vibrational coupling of bending and stretching modes, significantly enhanced above 10 GPa. Unconventional nature of dihydrogen bonds is confirmed by the frequency increase, blueshift, of NH stretching modes with pressure. A role of certain hydrogen mediated interactions in the process of dehydrogenation of ammonia borane and its alkali metal derivatives is speculated. Findings presented here call for reconsideration of hydrogen release mechanism from alkali metal ammonia borane derivatives. The work makes significant contribution towards establishing the general theory of ubiquitous and versatile hydrogen mediated interactions.

Barren Plateaus in Quantum Neural Network Training Landscapes

Abstract: Many experimental proposals for noisy intermediate scale quantum devices involve training a parameterized quantum circuit with a classical optimization loop. Such hybrid quantum-classical algorithms are popular for applications in quantum simulation, optimization, and machine learning. Due to its simplicity and hardware efficiency, random circuits are often proposed as initial guesses for exploring the space of quantum states. We show that the exponential dimension of Hilbert space and the gradient estimation complexity make this choice unsuitable for hybrid quantum-classical algorithms run on more than a few qubits. Specifically, we show that for a wide class of reasonable parameterized quantum circuits, the probability that the gradient along any reasonable direction is non-zero to some fixed precision is exponentially small as a function of the number of qubits. We argue that this is related to the 2-design characteristic of random circuits, and that solutions to this problem must be studied. Gradient-based hybrid quantum-classical algorithms are often initialised with random, unstructured guesses. Here, the authors show that this approach will fail in the long run, due to the exponentially-small probability of finding a large enough gradient along any direction.

Meso-Substituted Porphyrins for Dye-Sensitized Solar Cells

Abstract: Among the several approaches for harnessing solar energy and converting it into electricity, dye-sensitized solar cells (DSSC) represent one of the most promising methods for future large-scale power production from renewable energy sources. In these cells, the sensitizer is one of the key components harvesting solar radiation and converting it into electric current. The electrochemical, photophysical, and ground and excited state properties of the sensitizer play an important role for charge transfer dynamics at the semiconductor interface. Moreover, for long-term stability and practical applications, electrolytes based on the iodine/triiodine couple also suffer from two other disadvantages: the corrosive effect toward the metal electrodes, and the partial absorption of the visible light by triiodine anions. These issues hence constitute one of the reasons that have encouraged the development of alternative iodine-free redox couples in liquid electrolytes for DSSCs.

The rise of organic electrode materials for energy storage

Abstract: Organic electrode materials are very attractive for electrochemical energy storage devices because they can be flexible, lightweight, low cost, benign to the environment, and used in a variety of device architectures. They are not mere alternatives to more traditional energy storage materials, rather, they have the potential to lead to disruptive technologies. Although organic electrode materials for energy storage have progressed in recent years, there are still significant challenges to overcome before reaching large-scale commercialization. This review provides an overview of energy storage systems as a whole, the metrics that are used to quantify the performance of electrodes, recent strategies that have been investigated to overcome the challenges associated with organic electrode materials, and the use of computational chemistry to design and study new materials and their properties. Design strategies are examined to overcome issues with capacity/capacitance, device voltage, rate capability, and cycling stability in order to guide future work in the area. The use of low cost materials is highlighted as a direction towards commercial realization.

Nitrogen-Doped Porous Carbon Nanosheets Templated from g-C3 N4 as Metal-Free Electrocatalysts for Efficient Oxygen Reduction Reaction.

Abstract: Nitrogen-doped porous carbon nanosheets (N-CNS) are synthesized by hydrothermal carbon coating of g-C3 N4 nanosheets followed by high-temperature treatment in N2 . g-C3 N4 serves as a template, nitrogen source, and porogen in the synthesis. This approach yields N-CNS with a high nitrogen content and comparable oxygen reduction reaction catalytic activities to commercial Pt/C catalysts in alkaline media.