Density functional studies of molecular structures of N-methyl formamide, N,N-dimethyl formamide, and N,N-dimethyl acetamide

Density functional theory was applied to the calculation of molecular structures of N-methyl formamide (NMF), N,N-dimethyl formamide (DMF), and N,N-dimethyl acetamide (DMA). DFT calculations on NMF, DMF, and DMA were performed using a combination of the local functional of Vosko, Wilk, and Nusair (VWN) with the nonlocal exchange functional of Becke and the nonlocal correlational functional of Lee, Yang, and Parr (BLYP). The adiabatic connection method (ACM) of Becke has also been used, for the first time, for the calculation of molecular structures of NMF, DMF, and DMA. The calculated molecular structures are in excellent agreement with the experimental geometries of NMF and DMA derived from gas-phase electron-diffraction studies. Sparse experimental data on the gas-phase geometry of DMF reported in the literature compares well with the DFT results on DMF. DFT emerges as a powerful method to calculate molecular structures.     

Single specimen determination of Young's and bulk moduli of polymers

Summary A new method is presented for the rapid and consecutive determination of theYoung's and bulk moduli of polymeric solids in compression loading. Usually these properties are determined by separate measurements. However, by using an undersized specimen in a standard bulk compressibility tester, it is possible to determine both moduli on the same specimen in a single test procedure. Initial loading of the undersized specimen results in a decrease in length and an increase in diameter. From these changes,Young's modulus may be calculated. Once the bore of the tester is filled, the application of additional pressure results in a decrease in the volume of the polymer from which the bulk modulus may be calculated. Both determinations may be made within minutes. The moduli values are in general agreement with published values and the calculated values for Poisson's ratio fall into the expected range.

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Zusammenfassung Es wird eine neue Methode vorgestellt für die schnelle und fortlaufende Bestimmung des Elastizitäts- und Kompressions-Modul us polymerer Festkörper bei einer Druckbelastung. Normalerweise werden diese Eigenschaften durch unterschiedliche Methoden bestimmt. Durch Benutzung einer unterdimensionierten Probe in einem Standard-Kompressionsprüfgerät ist es möglich, beide Moduln an der gleichen Probe in einem einzigen Versuch zu ermitteln. Die Anfangsbelastung einer unterdimensionierten Probe führt zu einer Längenabnahme und einer Zunahme des Durchmessers. Aus diesen Änderungen läßt sich der Elastizitätsmodul berechnen. Sobald die Bohrung des Gerätes gefüllt ist, führt die Erhöhung des Druckes zu einer Volumen-Abnahme des Polymers, aus dem sich der Kompressionsmodul berechnen läßt. Beide Bestimmungen können in wenigen Minuten durchgeführt werden. Die Modulwerte stimmen im allgemeinen mit veröffentlichten Werten überein, und die für dasPoisson-Verhältnis ermittelten Werte liegen in dem erwarteten Bereich.

     

Hydrogenation, structure and magnetic properties of La(Fe0.91Si0.09)13 hydrides and deuterides

Hydrogenation, crystal structure and magnetic properties of La(Fe0.91Si0.09)13H(D)y have been studied by pressure-composition isotherms (PCI), X-ray diffraction (XRD), differential scanning calorimetry (DSC) and magnetization measurements. The maximum absorption capacity is found to be 1.9 H(D) atoms per formula unit as a solid solution. All hydrides and deuterides crystallize in the NaZn13-type cubic structure with the lattice parameter increasing linearly with H(D) concentration. The H(D) absorption enhances the Curie temperature significantly. The magnetic entropy change of the highly H-absorbed compound La(Fe0.91Si0.09)13H1.81 reaches ～26 J/kg·K under a magnetic field change of 5 T near the Curie temperature TC = 350 K. No observable isotope effect seems to imply that only the magnetovolume effect is responsible for the strong interplay between magnetism and lattice.     

Breather trapping and breather transmission in a DNA model with an interface

We study the dynamics of moving discrete breathers in an interfaced piecewise DNA molecule. This is a DNA chain in which all the base pairs are identical and there exists an interface such that the base pairs dipole moments at each side are oriented in opposite directions. The Hamiltonian of the Peyrard-Bishop model is augmented with a term that includes the dipole-dipole coupling between base pairs. Numerical simulations show the existence of two dynamical regimes. If the translational kinetic energy of a moving breather launched towards the interface is below a critical value, it is trapped in a region around the interface collecting vibrational energy. For an energy larger than the critical value, the breather is transmitted and continues travelling along the double strand with lower velocity. Reflection phenomena never occur. The same study has been carried out when a single dipole is oriented in opposite direction to the other ones. When moving breathers collide with the single inverted dipole, the same effects appear. These results emphasize the importance of this simple type of local inhomogeneity as it creates a mechanism for the trapping of energy. Finally, the simulations show that, under favorable conditions, several launched moving breathers can be trapped successively at the interface region producing an accumulation of vibrational energy. Moreover, an additional colliding moving breather can produce a saturation of energy and a moving breather with all the accumulated energy is transmitted to the chain.     

Magnetic interference patterns and vortices in diffusive SNS junctions

We study theoretically the electronic and transport properties of a diffusive superconductor-normal metal-superconductor junction in the presence of a perpendicular magnetic field. We show that the field dependence of the critical current crosses over from the well-known Fraunhofer pattern in wide junctions to a monotonic decay when the width of the normal wire is smaller than the magnetic length xi(H)=square root Phi(0)/H, where H is the magnetic field and Phi(0) the flux quantum. We demonstrate that this behavior is a direct consequence of the magnetic vortex structure appearing in the normal region and predict how this structure is manifested in the local density of states.     

Light‐Driven Reversible Alignment Switching of Liquid Crystals Enabled by Azo Thiol Grafted Gold Nanoparticles

Stimuli‐directed alignment control of liquid crystals (LCs) with desired molecular orientation is currently in the limelight for the development of smart functional materials and devices. Here, photoresponsive azo thiol (AzoSH) was grafted onto gold nanoparticles (GNPs). The resulting hybrid GNPs were able to homogeneously mix with a commercially available nematic LC host, as evidenced by Cryo‐TEM. Interestingly, the LC nanocomposites were found to undergo reversible alignment transition upon light irradiation as a consequence of the trans–cis photoisomerization of the azo groups on the GNP surface. LC molecules in either planar or bare glass cells were able to change their alignment to vertical upon UV irradiation, while the vertically aligned LC molecules returned to the planar or random orientation under visible irradiation. Neither the azo thiol molecules nor the unfunctionalized GNPs alone promoted the alignment of the LC molecules in the system upon light irradiation. The photoinduced vertical alignment without applied electric or magnetic field was very stable over time and with respect to temperature. Furthermore, an optically switchable device based on the photostimulated reversible alignment control of LCs was demonstrated.     

The role of induced current density in Steroelectronic effects: Perlin effect

The normal and reverse Perlin effect is usually explained by the redistribution of electron density produced by hyperconjugative mechanisms, which increases the electron population within axial or equatorial proton in normal or reverse effect, respectively. Here an alternative explanation for the Perlin effect is presented on the basis of the topology of the induced current density, which directly determines the nuclear magnetic shielding. Current densities around the C? H bond critical point and intra‐atomic and interatomic contributions to the magnetic shielding explain the observed Perlin effect. The balance between intra‐atomic and interatomic contributions determines the difference in the total atomic shielding. Normal Perlin effect is dominated by intra‐atomic part, whereas reverse effect is dominated by interatomic contribution. © 2015 Wiley Periodicals, Inc.     

Almost periodic and pseudo-almost periodic solutions to fractional differential and integro-differential equations

We study the existence of almost periodic (resp., pseudo-almost periodic) mild solutions for fractional differential and integro-differential equations in the case when the forcing term belongs to the class of Stepanov almost (resp., Stepanov-like pseudo-almost) periodic functions.