Generation and trapping of non-aromatic cycloimines via diazotization/dediazotization of N-amino cyclic amines: theoretical and experimental results

Structural Chemistry - A theoretical investigation of the model diazotization/dediazotization of N-aminopiperidine and N-aminomorpholine at the DFT (B3LYP/6-31+G(d)) level indicated that the...     

Omnidirectional reflector using nanoporous SiO2 as a low-refractive-index material

Triple-layer omnidirectional reflectors (ODRs) consisting of a semiconductor, a quarter-wavelength transparent dielectric layer, and a metal have high reflectivities for all angles of incidence. Internal ODRs (ambient material's refractive index n > 1.0) are demonstrated that incorporate nanoporous SiO2, a low-refractive-index material (n = 1.23), as well as dense SiO2 (n = 1.46). GaP and Ag serve as the semiconductor and the metal layer, respectively. Reflectivity measurements, including angular dependence, are presented. Calculated angle-integrated TE and TM reflectivities for ODRs employing nanoporous SiO2 are R(int)/TE = 99.9% and R(int)/TM = 98.9%, respectively, indicating the high potential of the ODRs for low-loss waveguide structures.     

Low-speed impact craters in loose granular media

We report on craters formed by balls dropped into dry, noncohesive, granular media. By explicit variation of ball density rho(b), diameter D(b), and drop height H, the crater diameter is confirmed to scale as the 1/4 power of the energy of the ball at impact: D(c) approximately equal (rho(b)D(3)(b)H)(1/4). Against expectation, a different scaling law is discovered for the crater depth: d approximately equal (rho(3/2)(b)D(2)(b)H)(1/3). The scaling with properties of the medium is also established. The crater depth has significance for granular mechanics in that it relates to the stopping force on the ball.     

Phonon frequency shift and effect of correlation on the electron-phonon interaction in heavy fermion systems

The electron-phonon interaction in the periodic Anderson model (PAM) is considered. The PAM incorporates the effect of onsite Coulomb interaction (U) between f-electrons. The influence of Coulomb correlation U on the phonon response of the system is studied by evaluating the phonon spectral function for various parameters of the model. The numerical evaluation of the spectral function is carried out in the long wavelength limit at finite temperatures keeping only linear terms in U. The observed behaviour is found to agree well with the general features obtained experimentally for some heavy fermion (HF) systems.     

On further application of r as a metric for validation of QSAR models

Validation is a crucial aspect for quantitative structure–activity relationship (QSAR) model development. External validation is considered, in general, as the most conclusive proof of predictive capacity of a QSAR model. In the absence of truly external data set, external validation is usually performed on test set compounds, which are members of the original data set but not used in model development exercise. In the case of small data sets, QSAR researchers experience problem in model development due to the fact that the developed models may be less reliable on account of the small number of training set compounds and such models may also show poor external predictability because the models may not have captured all necessary features required for the particular structure–activity relationships. The present paper attempts to show that ‘true r_(LOO)’ statistic calculated based on the model derived from the undivided data set with application of variable selection strategy at each cycle of leave‐one‐out (LOO) validation may reflect external validation characteristics of the developed model thus obviating the requirement of splitting of the data set into training and test sets. This approach may be helpful in the case of small data sets as it uses all available data for model development and validation thus making the resulting model more reliable. Copyright © 2009 John Wiley & Sons, Ltd.     

A transportation problem with fuzzy-stochastic cost

In this paper, we consider some transportation problems (TPs) with different types of fuzzy-stochastic unit transportation costs and budget constraints. These fuzzy stochastic costs are reduced to corresponding crisp ones in two different ways. For the first method, using the definition of α$\alpha$-cut of the fuzzy numbers, expectation is taken separately on both lower and upper α$\alpha$-cuts and then mean expectation is calculated with the help of signed distance. In the second procedure, we realize fuzzy random events (ξ?r)$(\xi ?r)$ and (ξ?r)$(\xi ?r)$ for the fuzzy random variable (ξ)$(\xi )$. Using credibility measure of these events, mean chances for the above fuzzy random events are calculated and then expectation is taken to get the crisp expressions. The reduced deterministic problems of the fuzzy stochastic TP are solved using a real coded genetic algorithm with Roulette wheel selection, arithmetic crossover and random mutation. Few numerical examples are demonstrated to find the optimal solutions of the proposed models.     

Molecular ordering of a cyano compound at a displacive transition temperature: a statistical analysis based on quantum mechanics and computer simulations

A statistical analysis has been carried out to determine the configurational preference of a pair of 4-cyanophenyl 4- n -pentylbenzoate (CPPB) molecules with respect to translatory and orientational motions. The CNDO/2 method has been employed to evaluate the net atomic charge and atomic dipole components at each atomic centre of the molecule. Configurational energy has been computed using the Rayleigh-Schodinger perturbation method. The total interaction energy values obtained through these computations were used to calculate the probability of each configuration at the phase transition temperature using the Maxwell-Boltzmann formula. An attempt has been made to identify the most probable configuration at the phase transition temperature. Further, the flexibility of various configurations has been studied in terms of variation of probability due to small departures from the most probable configuration. On the basis of stacking, in-plane and terminal interaction energy calculations, all possible geometrical arrangements of the molecular pair have been considered. The results are discussed in the light of experimental as well as theoretical observations. The nature of the mesophase has been correlated with the parameter introduced in this paper.     

Self-injection length in La0.7Ca0.3MnO3-YBa2Cu3O7-δ ferromagnet-superconductor multilayer thin films

We have carried out extensive studies on the self-injection problem in barrierless heterojunctions between La_0.7Ca_0.3MnO₃ (LCMO) and YBa₂Cu₃O_7-δ (YBCO) thin films. The heterojunctions were formed in situ by sequentially growing LCMO and YBCO films on 〈100〉 LaAlO₃ (LAO) substrate using a pulsed laser deposition (PLD) system. YBCO micro-bridges with 64 μm width were patterned both on the LAO (control) and LCMO side of the substrate. Critical current, I _c, was measured at 77 K on both the control side as well as the LCMO side for different YBCO film thickness. It was observed that while the control side showed a J _c of ∼ 2 × 10⁶ A/cm², the LCMO side showed about half the value for the same thickness (1800 ?). The difference in J _c indicates that a certain thickness of YBCO has become ‘effectively’ normal due to self-injection. From the measurement of J _c at two different thicknesses (1800 ? and 1500 ?) of YBCO films both on the LAO as well as the LCMO side, the value of self-injection length (at 77 K) was estimated to be ∼ 900 ?. To the authors’ best knowledge, this is the first time that self-injection length has been quantified. A control experiment carried out with LaNiO₃ deposited by PLD on YBCO did not show any evidence of self-injection.     

Gauging universe expansion via scalar fields

In this study, we investigate the expansion of the FRLW universe in the open, closed, and flat geometries. The universe is dominated by a scalar field (spatially homogeneous) as a source of dark energy. We consider the three different classes of scalar fields – quintessence, tachyonic, and phantom field – for our analysis. A mathematical analysis is carried out by considering these three scalar fields with exponential and power-law potentials. Both potentials give exponential expansion in the open, closed, and flat FRLW universes. It is found that quintessence, tachyonic, and phantom scalar fields are indistinguishable under the slow roll approximation.     

Study of magnetoresistance and conductance of bicrystal grain boundary in La0.67Ba0.33MnO3 thin film

La_0.67Ba_0.33MnO₃ (LBMO) thin film is deposited on a 36.7°C SrTiO₃ bicrystal substrate using laser ablation technique. A microbridge is created across bicrystal grain boundary and its characteristics are compared with a microbridge on the LBMO film having no grain boundary. Presence of grain boundary exhibits substantial magnetoresistance ratio (MRR) in the low field and low temperature region. Bicrystal grain boundary contribution in MRR disappears at temperature T>175 K. At low temperature, I-V characteristic of the microbridge across bicrystal grain boundary is nonlinear. Analysis of temperature dependence of dynamic conductance-voltage characteristics of the bicrystal grain boundary indicates that at low temperatures (T<175 K) carrier transport across the grain boundary in LBMO film is dominated by inelastic tunneling via pairs of manganese atoms and tunneling through disordered oxides. At higher temperatures (T>175 K), magnetic scattering process is dominating. Decrease of bicrystal grain boundary contribution in magnetoresistance with the increase in temperature is due to enhanced spin-flip scattering process.