Influence of ion–ion correlation on Na+ transport in Na2Ni2TeO6: molecular dynamics study

Molecular dynamics (MD) study of Na⁺ transport in Na₂Ni₂TeO₆ is performed systematically with varying strength of Na⁺–Na⁺ short range repulsions to understand the physical principle governing ion transport mechanism. Na⁺ diffusion is enhanced by nearly an order of magnitude with reduced Na⁺–Na⁺ short range repulsion within the studied range. A similar behavior is also observed in other systems, e.g., AgI and Na₂Zn₂TeO₆, where mobile ions are located closely. The Na⁺ ion occupancy in Na₂Ni₂TeO₆ shows a significant shift from Na1 to Na2 sites gaining some degree of correlation. The study also emphasizes how mobile ion size influences the ionic diffusion. The fresh insight such as microscopic migration pathways, energy barriers, and jumping mechanism of Na⁺ are derived from the study.     

A Triatomic Silicon(0) Cluster Stabilized by a Cyclic Alkyl(amino) Carbene

Reduction of the neutral carbene tetrachlorosilane adduct (cAAC)SiCl₄ (cAAC=cyclic alkyl(amino) carbene :C(CMe₂)₂(CH₂)N(2,6‐iPr₂C₆H₃) with potassium graphite produces stable (cAAC)₃Si₃, a carbene‐stabilized triatomic silicon(0) molecule. The Si?Si bond lengths in (cAAC)₃Si₃ are 2.399(8), 2.369(8) and 2.398(8) Å, which are in the range of Si?Si single bonds. Each trigonal pyramidal silicon atom of the triangular molecule (cAAC)₃Si₃ possesses a lone pair of electrons. Its bonding, stability, and electron density distributions were studied by quantum chemical calculations.     

Recognition of Artificial Nucleobases by E. coli Purine Nucleoside Phosphorylase versus its Ser90Ala Mutant in the Synthesis of Base‐Modified Nucleosides

A wide range of natural purine analogues was used as probe to assess the mechanism of recognition by the wild‐type (WT) E. coli purine nucleoside phosphorylase (PNP) versus its Ser90Ala mutant. The results were analyzed from viewpoint of the role of the Ser90 residue and the structural features of the bases. It was found that the Ser90 residue of the PNP 1) plays an important role in the binding and activation of 8‐aza‐7‐deazapurines in the synthesis of their nucleosides, 2) participates in the binding of α‐D ‐pentofuranose‐1‐phosphates at the catalytic site of the PNP, and 3) catalyzes the dephosphorylation of intermediary formed 2‐deoxy‐α‐D ‐ribofuranose‐1‐phosphate in the trans‐2‐deoxyribosylation reaction. 5‐Aza‐7‐deazaguanine manifested excellent substrate activity for both enzymes, 8‐amino‐7‐thiaguanine and 2‐aminobenzothiazole showed no substrate activity for both enzymes. On the contrary, the 2‐amino derivatives of benzimidazole and benzoxazole are substrates and are converted into the N1‐ and unusual N2‐glycosides, respectively. 9‐Deaza‐5‐iodoxanthine showed moderate inhibitory activity of the WT E. coli PNP, whereas 9‐deazaxanthine and its 2′‐deoxyriboside are weak inhibitors.     

Stabilization of Linear C3 by Two Donor Ligands: A Theoretical Study of L-C3-L (L=PPh3, NHCMe,cAACMe)**

Quantum chemical studies using density functional theory and ab initio methods have been carried out for the molecules L-C₃-L with L=PPh₃ ( 1 ), NHC^Me ( 2 , NHC=N-heterocyclic carbene), and cAAC^Me ( 3 , cAAC=cyclic (alkyl)(amino) carbene). The calculations predict that 1 and 2 have equilibrium geometries where the ligands are bonded with rather acute bonding angles at the linear C₃ moiety. The phosphine adduct 1 has a synclinal (gauche) conformation whereas 2 exhibits a trans conformation of the ligands. In contrast, the compound 3 possesses a nearly linear arrangement of the carbene ligands at the C₃ fragment. The bond dissociation energies of the ligands have the order 1 < 2 < 3 . The bonding analysis using charge and energy decomposition methods suggests that 3 is best described as a cumulene with electron-sharing double bonds between neutral fragments (cAAC^Me)₂ and C₃ in the respective electronic quintet state yielding (cAAC^Me)=C₃=(cAAC^Me). In contrast, 1 and 2 possess electron-sharing and dative bonds between positively charged ligands [(PPh₃)₂]⁺ or [(NHC^Me)₂]⁺ and negatively charged [C₃]⁻ fragments in the respective doublet state.     

Contrasting magnetic behavior of fine particles of some Kondo lattices

We have investigated the magnetic behavior of ball-milled fine particles of well-known Kondo lattices, CeAu₂Si₂, CePd₂Si₂ and CeAl₂, by magnetization and heat-capacity studies in order to understand the magnetic behavior when the particle size is reduced. These compounds have been known to order antiferromagnetically in the bulk form near ($T_N=$) 10, 10 and 3.8 K respectively. We find that the features due to magnetic ordering get suppressed to temperatures below 1.8 K in the case of fine particles of ternary alloys, though trivalence of Ce as inferred from the effective moment remains unchanged. In contrast to this, in CeAl₂, there appears to be a marginal enhancement of $T_N$, when the particle size is reduced to less than a micron. These results can be consistently understood by proposing that these compounds move toward left in the Doniach magnetic phase-diagram, for instance, due to relatively more 4f-localization, as the particle size is reduced.     

The nature of 4f electron magnetism in the diluted ferromagnetic Kondo lattice, CeIr2B2

We report on the physical properties of the series Ce(1-x)La(x)Ir(2)B(2) (x = 0-0.9), obtained by means of magnetization, heat capacity and electrical resistivity measurements as a function of temperature (down to 0.7 K for the latter two measurements). The Curie temperature of CeIr(2)B(2) (~5 K) is lowered due to La substitution, as expected. However, no quantum critical point or 'non-Fermi liquid' behavior was observed even in the dilute limit of x = 0.9. Interestingly, ferromagnetic ordering persists even for Ce(0.1)La(0.9)Ir(2)B(2), below 0.8 K. Among the Ce systems, CeIr(2)B(2) is one of the compounds in which direct 4f-4f interaction does not appear to play any role in the magnetism, which is controlled by the indirect exchange interaction alone. In this compound, the Kondo effect persists in the ferromagnetic ordered state, as inferred from the entropy data.     

Modified control grid interpolation for the volumetric reconstruction of fluid flows

Complex applications in fluid dynamics research often require more highly resolved velocity data than direct measurements or simulations provide. The advent of stereo PIV and PCMR techniques has advanced the state-of-the-art in flow velocity measurement, but 3D spatial resolution remains limited. Here a new technique is proposed for velocity data interpolation to address this problem. The new method performs with higher quality than competing solutions from the literature in terms of accurately interpolating velocities, maintaining fluid structure and domain boundaries, and preserving coherent structures.     

Spectroscopic Investigation of the Electronic Structure of YN: The XΣ Ground State and the New B1, C1 and D1 Excited Electronic States

YN molecules were produced in a free jet molecular beam apparatus by a laser vaporizing yttrium metal in the presence of He doped with NH₃. Laser excitation spectra were observed in the range 18 250-19 850 cm⁻¹. The ground state was confirmed to have ¹Σ⁺ symmetry. The fundamental vibration in the ground state was measured to be 650.6(1) cm⁻¹. Three new electronic states, B1, C1, and D1, were observed at 18 974.7(1), 19 023.3(1), and 19 824.0(1) cm⁻¹, respectively. The fundamental vibrations and equilibrium internuclear distances were found to be 718.3(1) cm⁻¹ and 1.939(8) for the B1 state and 723.5(1) cm⁻¹ and 1.9194(3) for the C1 state. Two additional electronic states were identified with the help of a deperturbation procedure, one of which is either the ¹Σ⁺ or the ³Σ₀⁻ state. The newly observed electronic states cannot be accounted for based on the existing ab initio results. We expect that these states correlate with the excited asymptote Y(4d¹5s²²D)+N(²D).