Geometries and NMR properties of cisplatin and transplatin revisited at the four-component relativistic level

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Synthesis and Crystal Structure of LiY(CN2)2, Having a Structure Related to That of NiAs

The new ternary carbodiimide LiY(CN₂)₂ was synthesized by solid state metathesis reaction between YF₃ and Li₂(CN₂) in a silica tube at 550 °C. The X‐ray single‐crystal structure determination yielded an orthorhombic crystal system (Pbcn, Z = 4, a = 982.0(3), b = 698.5(2), c = 613.4(2) pm). The crystal structure can be considered related to the NiAs structure. The carbodiimide ions are arranged in layers following the motif of a hexagonal closest packing of sticks. Lithium and yttrium cations occupy all octahedral voids in an ordered fashion, alternating on top of each other along the hcp stacking direction.     

Nitrous Oxide Adsorption and Decomposition on Zeolites and Zeolite-like Materials

Decomposition of N₂O on modified zeolites, crystalline titanosilicalites, and related amorphous systems is studied by the catalytic and spectroscopic methods. Zinc-containing HZSM-5 zeolites and titanosilicalites with moderate Ti/Si ratios are shown to exhibit a better catalytic performance in N₂O decomposition as compared with conventionally used Cu/HZSM-5 zeolites and amorphous Cu-containing catalysts. Dehydroxylation of the HZSM-5 zeolite by calcination at 1120 K results in an enhancement of the N₂O conversion. The mechanism of the reaction and the role of coordinatively unsaturated cations and Lewis acid sites in N₂O decomposition are discussed on the basis of the spectroscopic data.     

New concepts in the physics and chemistry op solid polymers fracture

Elementary events in polymer fracture at the molecular level are the breakdowns of single polymeric chains. Breakdown of a stretched macromolecule is accompanied by its mechanical degradation. Comparison of experimental data on the molecular products of thermal and mechanical degradation points to significant distinctions between these two processes. Generation of highly excited (“hot”) molecular products of mechanical degradation by the growing crack cannot be explained in terms of the kinetic concept of polymer fracture. Elaborate theoretical analysis of polymeric chain breakdown and generation of “hot” molecular products in subpicosecond time range is made by numerical molecular dynamic simulation with a computer. The mechanisms of primary and secondary chain breakdowns are established. The principal initiators of breakdowns are localized nonlinear modes of the lattice soliton type. Generation of highly excited (“hot”) molecular products occurs at the initial stage of mechanical degradation (during≈1 picosecond after the first breakdown).     

A Maximal Correlation Framework for Fair Machine Learning

As machine learning algorithms grow in popularity and diversify to many industries, ethical and legal concerns regarding their fairness have become increasingly relevant. We explore the problem of algorithmic fairness, taking an information–theoretic view. The maximal correlation framework is introduced for expressing fairness constraints and is shown to be capable of being used to derive regularizers that enforce independence and separation-based fairness criteria, which admit optimization algorithms for both discrete and continuous variables that are more computationally efficient than existing algorithms. We show that these algorithms provide smooth performance–fairness tradeoff curves and perform competitively with state-of-the-art methods on both discrete datasets (COMPAS, Adult) and continuous datasets (Communities and Crimes).     

Revisiting the Synthesis of Functionally Substituted 1,4-Dihydrobenzo[e][1,2,4]triazines

A series of novel 1,4-dihydrobenzo[1,2,4][e]triazines bearing an acetyl or ester moiety as a functional group at the C(3) atom of the 1,2,4-triazine ring were synthesized. The synthetic protocol is based on an oxidative cyclization of functionally substituted amidrazones in the presence of DBU and Pd/C. It was found that the developed approach is suitable for the preparation of 1,4-dihydrobenzo[e][1,2,4]triazines, but the corresponding Blatter radicals were isolated only in few cases. In addition, a previously unknown dihydrobenzo[e][1,2,4]triazolo[3,4-c][1,2,4]triazine tricyclic open-shell derivative was prepared. Studies of thermal behavior of the synthesized 1,4-dihydrobenzo[1,2,4][e]triazines revealed their high thermal stability (up to 240–250 °C), which enables their application potential as components of functional organic materials.     

Electron Transport in Configurational Model of Ferromagnetic Fulleride with Triple Orbital Degeneracy

Abstract

Phenomenon of ferromagnetic ordering was for a long time associated exclusively with transition metal and rare-earth compounds. Nowadays this view is challenged by growing evidence that in molecular carbon-based systems the ferromagnetic alignment of spins can be observed as well. We have developed a microscopical model of a fulleride electronic subsystem taking into account triple orbital degeneracy of energy states within the configurational-operator approach. Using the Green function method the energy spectrum of the model has been calculated. Conditions for the ferromagnetic state stabilization have been determined. Static electrical conductivity and effective masses of current carriers in the system with orbitally degenerated energy band have been obtained. In the ground state and for low temperatures at different forms of unperturbed density of electronic states the concentration dependences of transport characteristics for less-then-half-filled lower quasiparticle subband have been calculated.     

Low dose 60Co gamma-irradiation effects on electronic carrier transport and DC characteristics of AlGaN/GaN high-electron-mobility transistors

The impact of internal irradiation with secondary Compton electrons, generated by gamma-photons, on the characteristics of III-N/GaN-based devices was explored. N-channel AlGaN/GaN high-electron-mobility transistors (HEMTs) were exposed to gamma-radiation from a ⁶⁰Co source for doses up to 600?Gy. Temperature-dependent electron beam-induced current (EBIC) was employed to measure minority carrier transport properties. For low doses below ～250?Gy, the minority carrier diffusion length in AlGaN/GaN HEMTs is shown to increase by about 40%. This increase is likely due to longer minority carrier lifetime induced by internal Compton electron irradiation. An associated decrease in activation energy, extracted from temperature-dependent EBIC, was also found. The obtained increase in transconductance and decrease in gate leakage current indicate an improvement in performance of the devices after low doses of irradiation. For high doses of gamma-irradiation, above ～300?Gy, the performance of HEMTs showed a deterioration. The deterioration results from the onset of increased carrier scattering due to additional radiation-induced defects, as is translated in a decrease of minority carrier diffusion length.