Illumination with Ultraviolet or Visible Light Induces Chemical Changes in the Water-soluble Manganese Complex, [Mn4O6(bpea)4]Br4

We measured the photosensitivity of an artificial tetranuclear oxo–Mn(IV) complex, [Mn₄O₆(bpea)₄]Br₄, which has an adamantane-shaped {Mn₄O₆}⁴⁺ core. Illumination caused changes in the absorption spectrum of the compound consistent with a one-electron reduction in the compound. Bromide appears to be the most probable electron donor in the reaction system. Chemical modification of the cluster appears to destabilize it, predisposing it to reductive degradation. UV light was more efficient than visible light in causing the changes. The data support the suggestion that the natural oxygen-evolving Mn complex is photosensitive and can oxidize components of the oxygen-evolving complex in its excited state causing photoinhibition, and that photostability is an important issue in designing Mn complexes for artificial photosynthesis. Furthermore, light-induced oxidation of bromide by [Mn₄O₆(bpea)₄]⁴⁺ may suggest that oxidation of chloride is involved in natural water splitting or has been involved during the evolution of the water-splitting enzyme.     

Mutual influence of uniaxial tensile strain and point defect pattern on electronic states in graphene

The study deals with electronic properties of uniaxially stressed mono- and multi-layer graphene sheets with various kinds of imperfection: point defects modelled as resonant (neutral) adsorbed atoms or molecules, vacancies, charged impurities, and local distortions. The presence of randomly distributed defects in a strained graphene counteract the band-gap opening and even can suppress the gap occurs when they are absent. However, impurity ordering contributes to the band gap appearance and thereby re-opens the gap being suppressed by random dopants in graphene stretched along zigzag-edge direction. The band gap is found to be non-monotonic with strain in case of mutual action of defect ordering and zigzag deformation. Herewith, the minimal tensile strain required for the band-gap opening (≈12.5%) is smaller than that for defect-free graphene (≈23%), and band gap energy reaches the value predicted for maximal nondestructive strains in the pristine graphene. Effective manipulating the band gap in graphene requires balanced content of ordered dopants: their concentration should be sufficient for a significant sublattice asymmetry effect, but not so much that they may suppress the band gap or transform it into the “quasi- (or pseudo-) gap”.     

Spin Hamiltonian, competing small energy scales, and incommensurate long-range order in the highly frustrated Gd(3)Ga(5)O(12) garnet antiferromagnet

Despite the availability of a spin Hamiltonian for the Gd(3)Ga(5)O(12) garnet (GGG) for over 25 years, there has so far been little theoretical insight regarding the many unusual low temperature properties of GGG. Here we investigate GGG in zero magnetic field using mean-field theory. We reproduce the spin liquid-like correlations and, most importantly, explain the positions of the sharp peaks seen in powder neutron diffraction experiments. We show that it is crucial to treat accurately the long-range nature of the magnetic dipolar interactions to allow for a determination of the small exchange energy scales involved in the selection of the experimental ordering wave vector. Our results show that the incommensurate order in GGG is classical in nature, intrinsic to the microscopic spin Hamiltonian and not caused by weak disorder.     

On scatteredly continuous maps between topological spaces

A map f:X→Y between topological spaces is defined to be scatteredly continuous if for each subspace AX the restriction f|A has a point of continuity. We show that for a function f:X→Y from a perfectly paracompact hereditarily Baire Preiss–Simon space X into a regular space Y the scattered continuity of f is equivalent to (i) the weak discontinuity (for each subset AX the set D(f|A) of discontinuity points of f|A is nowhere dense in A), (ii) the piecewise continuity (X can be written as a countable union of closed subsets on which f is continuous), (iii) the G_δ-measurability (the preimage of each open set is of type G_δ). Also under Martin Axiom, we construct a G_δ-measurable map f:X→Y between metrizable separable spaces, which is not piecewise continuous. This answers an old question of V. Vinokurov.     

High‐pressure Raman spectroscopy study of α and γ polymorphs of AlH3

For the first time, Raman spectroscopy of α and γ polymorphs of AlH₃ has been performed in the pressure range from ambient up to 16.9 and 32.7 GPa, respectively using the diamond anvil cell (DAC) technique. An analysis of pressure response wavenumbers (ν) for α‐AlH₃ showed a change of dν_i/dP at a pressure of about 8 GPa and may indicate a monoclinic distortion from the initially hexagonal α‐AlH₃. The distortion is stable at least up to 16.9 GPa. The γ form exhibited more complex behavior transforming to the α form at a pressure of about 12 GPa. The structural phase transition was shown to be an irreversible and kinetically slow process that required at least 5 h to complete. Copyright © 2008 John Wiley & Sons, Ltd.     

Dy2Ti2O7 spin ice: a test case for emergent clusters in a frustrated magnet

Dy2Ti2O7 is a geometrically frustrated magnetic material with a strongly correlated spin ice regime that extends from 1 K down to as low as 60 mK. The diffuse elastic neutron scattering intensities in the spin ice regime can be remarkably well described by a phenomenological model of weakly interacting hexagonal spin clusters, as invoked in other geometrically frustrated magnets. We present a highly refined microscopic theory of Dy2Ti2O7 that includes long-range dipolar and exchange interactions to third nearest neighbors and which demonstrates that the clusters are purely fictitious in this material. The seeming emergence of composite spin clusters and their associated scattering pattern is instead an indicator of fine-tuning of ancillary correlations within a strongly correlated state.     

2D quantum spin models and Jordan-Wigner fermions

We apply the 2D Jordan-Wigner fermionization to examine the ground state and thermodynamic properties of the square-lattice s=1/2 anisotropic XY model. We compare our findings with the results of different analytical and numerical approaches.     

Magnetic circular dichroism and computational study of mononuclear and dinuclear iron(iv) complexes

High-valent iron(iv)-oxo species are key intermediates in the catalytic cycles of a range of O₂-activating iron enzymes. This work presents a detailed study of the electronic structures of mononuclear ([Fe^IV(O)(L)(NCMe)]²⁺, 1, L = tris(3,5-dimethyl-4-methoxylpyridyl-2-methyl)amine) and dinuclear ([(L)Fe^IV(O)(μ-O)Fe^IV(OH)(L)]³⁺, 2) iron(iv) complexes using absorption (ABS), magnetic circular dichroism (MCD) spectroscopy and wave-function-based quantum chemical calculations. For complex 1, the experimental MCD spectra at 2–10 K are dominated by a broad positive band between 12 000 and 18 000 cm^–1. As the temperature increases up to ∼20 K, this feature is gradually replaced by a derivative-shaped signal. The computed MCD spectra are in excellent agreement with experiment, which reproduce not only the excitation energies and the MCD signs of key transitions but also their temperature-dependent intensity variations. To further corroborate the assignments suggested by the calculations, the individual MCD sign for each transition is independently determined from the corresponding electron donating and accepting orbitals. Thus, unambiguous assignments can be made for the observed transitions in 1. The ABS/MCD data of complex 2 exhibit ten features that are assigned as ligand-field transitions or oxo- or hydroxo-to-metal charge transfer bands, based on MCD/ABS intensity ratios, calculated excitation energies, polarizations, and MCD signs. In comparison with complex 1, the electronic structure of the Fe^IV O site is not significantly perturbed by the binding to another iron(iv) center. This may explain the experimental finding that complexes 1 and 2 have similar reactivities toward C–H bond activation and O-atom transfer.     

Joint spectroscopic and theoretical investigations of transition metal complexes involving non-innocent ligands

A series of transition metal complexes involving non-innocent o-dithiolene and o-phenylenediamine ligands has been characterized in detail by various spectroscopic methods like magnetic circular dichroism (MCD), absorption (abs), resonance Raman (rR), electron paramagnetic resonance (EPR), and sulfur K-edge X-ray absorption spectroscopies. A computational model for the electronic structure of the complexes is then proposed based on the density functional theory (DFT) or ab-initio methods, which can successfully account for the observed trends in the experimental spectra (MCD, rR, and abs) of the complexes. Based on these studies, the innocent vs non-innocent nature of the ligands in a given transition metal complex is found to be dependent on the position of the central metal ion in the periodic table, its effective nuclear charge in interplay with relativistic effects.     

Information Bottleneck Classification in Extremely Distributed Systems

We present a new decentralized classification system based on a distributed architecture. This system consists of distributed nodes, each possessing their own datasets and computing modules, along with a centralized server, which provides probes to classification and aggregates the responses of nodes for a final decision. Each node, with access to its own training dataset of a given class, is trained based on an auto-encoder system consisting of a fixed data-independent encoder, a pre-trained quantizer and a class-dependent decoder. Hence, these auto-encoders are highly dependent on the class probability distribution for which the reconstruction distortion is minimized. Alternatively, when an encoding–quantizing–decoding node observes data from different distributions, unseen at training, there is a mismatch, and such a decoding is not optimal, leading to a significant increase of the reconstruction distortion. The final classification is performed at the centralized classifier that votes for the class with the minimum reconstruction distortion. In addition to the system applicability for applications facing big-data communication problems and or requiring private classification, the above distributed scheme creates a theoretical bridge to the information bottleneck principle. The proposed system demonstrates a very promising performance on basic datasets such as MNIST and FasionMNIST.