Investigation of modification of hydrogenation and structural properties of LaNi5 intermetallic compound induced by substitution of Ni by Pd

The hydrogenation properties of the LaNi₅ (CaCu₅ type, hP6, P6/mmm) and Pd substituted derivatives LaNi_5−xPd_x compounds have been studied in the whole homogeneity range of the solid solution (0.25≤x≤1.5). The pressure versus hydrogen content isotherms show several plateaus and an increase of the plateau pressure as a function of palladium concentration. The volume increase of the Pd substituted alloys should have resulted in a lowering, and not an increase, of the plateau pressure, according to the conventional models based on the size effect. In order to elucidate the origin of this anomalous behavior, both an experimental and a theoretical ab initio electronic structure investigation have been carried out. Experimentally, the nature and the structural properties of the hydrides have been studied by both in situ and ex situ neutron diffraction. The crystal structures of the three hydride phases are reported (LaNi_3.5Pd_1.5D_1.96, filled-up CaCu₅ type, P6/mmm; LaNi₄PdD_2.72, LaNi₂(Ni_0.75Pt_0.25)₃H_2.61 type, oI128, Ibam; LaNi_4.75Pd_0.25D_5.67, partly ordered CaCu₅ type, P6mm). In addition, the phase diagram of LaNi_5−xPd_x-H system has been investigated. The electronic and thermodynamic properties of both intermetallic compounds and the hydrides have been studied by ab initio electronic structure calculations. The theoretical results are in good agreement with our experimental data, and show that electronic interactions play a major role in the hydrogenation behavior of these Pd substituted intermetallic compounds, and that these effects cannot be accounted for by a simplistic model based on the size effect alone.     

Weak Noncovalent Interactions in Three Closely Related Adamantane-Linked 1,2,4-Triazole N-Mannich Bases: Insights from Energy Frameworks,Hirshfeld Surface Analysis,In Silico 11β-HSD1 Molecular Docking and ADMET Prediction

Structural analysis and docking studies of three adamantane-linked 1,2,4-triazole N-Mannich bases (1–3) are presented. Compounds 1, 2 and 3 crystallized in the monoclinic P2₁/c, P2₁ and P2₁/n space groups, respectively. Crystal packing of 1 was stabilized by intermolecular C-H⋯O interactions, whereas compounds 2 and 3 were stabilized through intermolecular C-H⋯N, C-H⋯S and C-H⋯π interactions. The energy frameworks for crystal structures of 1–3 were described. The substituent effect on the intermolecular interactions and their contributions were described on the basis of Hirshfeld surface analyses. The 11β-hydroxysteroid dehydrogenase type 1 (11β-HSD1) inhibition potential, pharmacokinetic and toxicity profiles of compounds 1–3 were determined using in silico techniques. Molecular docking of the compounds into the 11β-HSD1 active site showed comparable binding affinity scores (−7.50 to −8.92 kcal/mol) to the 11β-HSD1 co-crystallized ligand 4YQ (−8.48 kcal/mol, 11β-HSD1 IC₅₀ = 9.9 nM). The compounds interacted with key active site residues, namely Ser170 and Tyr183, via strong hydrogen bond interactions. The predicted pharmacokinetic and toxicity profiles of the compounds were assessed, and were found to exhibit excellent ADMET potential.     

Luminescence self-quenching in Tm3+: YLF crystals: II. The luminescence decay and macrorates of energy transfer

Microparameters of migration and self-quenching of luminescence from the (³ P ₀, ¹ I ₆) levels of Tm ³⁺ ions are calculated and the luminescence decay from the ³ H ₄, ¹ G ₄, and ¹ _{D 2} levels are analyzed in the concentration series of LiY_1?x Tm_xF₄(x=0.5–10 at. %) crystals upon weak selective excitation. It is shown that the luminescence decay of a thulium ion concentration higher than 0.5 at. % cannot be described by the energy transfer that takes into account only the dipole-dipole interaction. The comparison of experimental kinetic curves with theoretical curves calculated within the framework of the known energy transfer models showed that multipole-multipole interaction is responsible for the self-quenching of the thulium levels. Contributions of higher multipole interactions to the self-quenching are estimated. The decay of luminescence from the ³ H ₄, ¹ G ₄, and ¹ D ₂ levels of Tm³⁺:YLF crystals with different concentrations of thulium ions is described analytically.     

Preparation and characterization of MgB2 superconductor

The MgB₂ superconductor, synthesized using solid-state and liquid-phase sintering methods, have been characterized for various properties. The upper critical field, irreversibility line and critical current density have been determined using magnetization data. The current-voltage characteristics recorded under an applied magnetic field revealed the existence of vortex glass transition. The surface analysis using X-ray photoelectron spectroscopy shows that MgB₂ is sensitive to atmospheric degradation.     

Tuning Colloidal Interactions Through Coordination Chemistry

The present work addresses the question of the range and amplitude of bridging attraction that is induced between surfactant micelles functionalized with complexing groups in the presence of coordination centers. An alkylethoxylated ester phosphate (AEP) is synthesized from a non‐ionic surfactant and anchored into DTAB micelles. In the absence of any coordination center, functionalized micelles repel each other. Phase behavior, dynamic light scattering and small angle neutrons scattering (SANS) experiments show that this repulsive interaction is switched to attractive by the addition of coordination centers such as aluminum cations. The extent of the composition range of coexisting phase depends on the concentration of coordination center and on the pH. Analysis of the structure factor obtained from SANS shows that the range of attraction is determined by the molecular dimension of the chelating surfactant, while the depth can be tuned with the concentration of coordination center and the pH. The strong influence of the pH is interpreted as arising from the condensation of aluminium cations that lead to high functional polynuclear complexes.     

Theoretical study of the decomposition reactions in substituted nitrobenzenes

The influence of substituent nature and position on the unimolecular decomposition of nitroaromatic compounds was investigated using the density functional theory at a PBE0/6-31+G(d,p) level. As the starting point, the two main reaction paths for the decomposition of nitrobenzene were analyzed: the direct carbon nitrogen dissociation (C6H5 + NO2) and a two step mechanism leading to the formation of phenoxyl and nitro radicals (C6H5O + NO). The dissociation energy of the former reaction was calculated to be 7.5 kcal/mol lower than the activation energy of the second reaction. Then the Gibbs free energies were computed for 15 nitrobenzene derivatives characterized by different substituents (nitro, methyl, amino, carboxylic acid, and hydroxyl) in the ortho, meta, and para positions. In meta position, no significant changes appeared in the reaction energy profiles whereas ortho and para substitutions led to significant deviations in energies on the decomposition mechanisms due to the resonance effect of the nitro group without changing the competition between these mechanisms. In the case of para and meta substitutions, the carbon-nitro bond dissociation energy has been directly related to the Hammett constant as an indicator of the electron donor-acceptor effect of substituents.     

Classroom note: A simple non-trivial student model of a bouncing soccer ball

When students have made some progress in studying ordinary differential equations (ODEs) during a semester, small groups are given a soccer ball and asked to determine the simplest model describing one bounce of the ball from shoulder height. To start with, they play with the ball. However, after a few weeks, they begin to ask penetrating questions and they are led to a simple model that has a non-trivial twist to the solution.     

Spectroscopic study of double sodium-yttrium fluoride crystals doped with erbium Na<Subscript>0.4</Subscript>Y<Subscript>0.6</Subscript>F<Subscript>2.2</Subscript>:Er<Superscript>3+</Superscript>: I. Intensities of luminescence spectra and kinetics of luminescence

Na_0.4Y_0.6F_2.2:Er³⁺ (NYF:Er) crystals with an erbium concentration as high as 100 at. % (Na_0.4Er_0.6F_2.2) were grown by the Bridgman-Stockbarger method. The optical spectra were investigated at low (6 K) and room temperatures. It is shown that the absorption spectrum of NYF:Er crystals contains wide bands (790–801 and 965–980 nm) corresponding to the emission range of laser diodes. The peak absorption cross section σ_a for the band peaked at λ=970.4 nm is 0.15×10^?20 cm². On the basis of the analysis of the absorption and luminescence spectra at low (6 and 12 K) temperatures, the structure of the Stark splitting of erbium levels was determined as a structure of quasi-centers for which Stark components are inhomogeneously broadened. The oscillator strengths of the transitions from the ground state of erbium to excited multiplets were calculated from the absorption spectra measured at T=300 K, and the intensity parameters Ω_t were determined by the Judd-Ofelt method: Ω₂=1.65×10^?20 cm², Ω₄=0.56× 10^?20 cm², and Ω₆=1.01×10^?20 cm². These values of the intensity parameters were used to calculate the probabilities of radiative transitions and the branching ratios. The rates of multiphonon nonradiative transitions in NYF: Er were estimated. The luminescence decay kinetics for radiative levels of erbium ions upon their selective excitation by nanosecond laser pulses was studied. The intracenter lifetimes of radiative levels of erbium ions were determined from the luminescence kinetics upon selective ion excitation by low-intensity light in a sample with a low erbium concentration (0.5%). It is demonstrated that, with an increase in temperature from 6 to 300 K, luminescence from the ⁴ G _11/2, ² G(H)_9/2, and ⁴ F _9/2 levels is quenched as a result of multiphonon nonradiative transitions. Luminescence from the ⁴ I _9/2 level is quenched only insignificantly with increasing temperature, and no quenching of luminescence from the ⁴ I _11/2 and ⁴ I _13/2 levels is observed. The spectra of steady-state luminescence of NYF:Er(0.5–15%) crystals were investigated upon broadband excitation by UV and UV-visible lamp light and selective time-resolved laser excitation. It is shown that low-lying levels of erbium ions separated by an energy gap smaller than 2500 cm^?1 are populated via cascade mechanisms. On the basis of the results obtained, it is concluded that NYF:Er ³⁺ crystals are promising candidates for active media of tunable diode-pumped lasers.     

A theoretical investigation of structural,mechanical, electronic and thermoelectric properties of orthorhombic CH<Subscript>3</Subscript>NH<Subscript>3</Subscript>PbI<Subscript>3</Subscript>

The structural, mechanical, electronic and thermoelectric properties of the low temperature orthorhombic perovskite phase of CH₃NH₃PbI₃ have been investigated using density functional theory (DFT). Elastic parameters bulk modulus B, Young’s modulus E, shear modulus G, Poisson’s ratio ν and anisotropy value A have been calculated by the Voigt–Reuss–Hill averaging scheme. Phonon dispersions of the structure were investigated using a finite displacement method. The relaxed system is dynamically stable, and the equilibrium elastic constants satisfy all the mechanical stability criteria for orthorhombic crystals, showing stability against the influence of external forces. The lattice thermal conductivity was calculated within the single-mode relaxation-time approximation of the Boltzmann equation from first-principles anharmonic lattice dynamics calculations. Our results show that lattice thermal conductivity is anisotropic, and the corresponding lattice thermal conductivity at 150 K was found to be 0.189, 0.138, and 0.530 Wm^?1K^?1 in the a, b, and c directions. Electronic structure calculations demonstrate that this compound has a DFT direct band gap at the gamma point of about 1.57 eV. The electronic transport properties have been calculated by solving the semiclassical Boltzmann transport equation on top of DFT calculations, within the constant relaxation time approximation. The Seebeck coefficient S is almost constant from 50 to 150 K. At temperatures 100 and 150 K, the maximal figure of merit is found to be 0.06 and 0.122 in the direction of the c-axis, respectively.