三氮宾分子的磁性设计

采用量子化学ＧＡＵＳＳＩＡＮ９４ａｂｉｎｉｔｉｏＵＨＦ方法和ＳＴＯ－３Ｇ基组设计一系列三氮宾分子，讨论分子的几何结构和取代基对其磁性的影响，计算结果表明，这些分子都具有铁磁性并有高自旋基态，有效交换积分值随代基的变化而变化，其中一种具有较代的总能量和高的有效交换积分值的分子，可期望被合成。     

Non-isothermal crystallization kinetics of poly(trimethylene terephthalate)/poly(ethylene 2,6-naphthalate) blends

The glass-transition temperature and non-isothermal crystallization of poly(trimethylene terephthalate)/poly(ethylene 2,6-naphthalate) (PTT/PEN) blends were investigated by using differential scanning calorimeter (DSC). The results suggested that the binary blends showed different crystallization and melting behaviors due to their different component of PTT and PEN. All of the samples exhibited a single glass-transition temperature, indicating that the component PTT and PEN were miscible in amorphous phase. The value of T_g predicted well by Gordon-Taylor equation decreased gradually with increasing of PTT content. The commonly used Avrami equation modified by Jeziorny, Ozawa theory and the method developed by Mo were used, respectively, to fit the primary stage of non-isothermal crystallization. The kinetic parameters suggested that the PTT content improved the crystallization of PEN in the binary blend. The crystallization growth dimension, crystallization rate and the degree of crystallinity of the blends were increased with the increasing content of PTT. The effective activation energy calculated by the advanced iso-conversional method developed by Vyazovkin also concluded that the value of E_a depended not only on the system but also on temperature, that is, the binary blend with more PTT component had higher crystallization ability and the crystallization ability is increased with increasing temperature. The kinetic parameters U^* and K_g were also determined, respectively, by the Hoffman-Lauritzen theory.     

Monte—Carlo model of the diffusion-limited reaction kinetics in microheterogeneous media. Comparison with the experimental plots of the forward and backward electron phototransfer kinetics on the pore diameter in silica gel

The kinetics of the diffusion-limited decay reaction A + B B was simulated by the Monte—Carlo method on a two-dimensional square lattice with defects presented by randomly distributed sites. The cases were considered where [B] [A] at the random initial distribution (quenching reaction) and [B] = [A] with the initial distribution of the A and B particles on neighboring sites (geminate recombination). The kinetic curves were approximated by the simplest analytical equation [A]/[A]₀ = (1 – )exp[–(kt)^1–h ] + (where k and are constants). The plots of the heterogeneity parameter (h) and time-averaged first-order rate constant vs. concentration of defects (p) or B particles (in the case of quenching) were obtained and compared with similar correlations obtained earlier by the experimental study of the kinetics of forward (quenching reaction) and backward (geminate recombination) electron phototransfer on the surface of different porous silica gels. The experimental plots of h vs. silica gel porosity are in satisfactory agreement with the plots of h vs. p in the model space, if the fraction of volume inaccessible for reactants, calculated from the free silica gel volume, is chosen as the p parameter for silica gel.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1536–1541, August, 2004.     

Effect of column diameter on efficiency in capillary supercritical fluid chromatography

Fused silica capillary columns with internal diameters from 100 to 25 μm were coated with SE-54 and evaluated under supercritical fluid chromatographic conditions using carbon dioxide as mobile phase. Experimental results compared well with theoretical predictions. At ten times the optimum mobile phase velocity and for a capacity factor, k of 3, efficiencies of 2300 to 5600 plates m^?1 were obtained for column diameters of 100 to 25 μm, respectively.     

On the solution characterization of an all-aromatic liquid-crystalline copolyester

Solution characterization of the thermotropic liquid–crystalline copolyester synthesized from terephthalic acid, phenyl hydroquinone, and (1-phenylethyl) hydroquinone (2 : 1 : 1) has been performed. Viscometry, size exclusion chromatography, and light scattering have been carried out under the optimal conditions found for measurement: 85°C in a 50/50 mixture by weight of phenol/1,2,4-trichlorobenzene. The absolute weight-average molecular weight from light-scattering measurements served for calibration of indirect methods of charac-terization (e.g., the limiting viscosity number [η] is related to the molecular weight by [η] = 5.10 × 10^?4 M_w^0.72), and the molecular weight per unit chain length, $ \bar M_L * $, from light scattering and size exclusion chromatography (SEC) is found to be 28 Å^?1, consistent with theoretical expectations. The calculated persistence length q is 28 Å. Moreover, the meth-odology of SEC characterization enables the kinetics of solid-state postpolymerization of this liquid-crystalline copolyester to be studied. © 1993 John Wiley & Sons, Inc.     

Use of small diameter WCOT columns for ultra-high resolution GC/MS

For clinical and environmental analyses utilizing capillary gas chromatography/mass spectrometry (GC/MS), increased sensitivity and speed of analysis are highly desirable. These performance advantages are realized using a WCOT column of 100 μm i.d. as compared to the more conventional 200 μm i.d. capillary columns. The improved sensitivity of capillary direct GC/MS with the 100 μm i.d. column for the confirmation of drugs of abuse will be demonstrated. For environmental analysis, the superior efficiency and resolution of the 100 μm i.d. column can be employed for the separation of priority pollutants. This approach is more amenable to capillary direct GC/MS providing a more effective interface to the mass spectrometer. As a result improved sensitivity and a considerable decrease in analysis time is achieved over that obtained with the larger diameter environmental specialty phase columns.     

A relaxation times coupling method to construct acoustic relaxation calibration for two-frequency measuring gas compositions

In our previous work (Hu et al., 2014), a method has been proposed to detect gas compositions by locating the acoustic spectral peaks, which can be detected only by two-frequency acoustic measurements in practice. However, as a ‘Detection Calibration’, the effective relaxation area (ERA) constructed by existing theoretical model cannot match the two-frequency measurements when there are more than one strong relaxational components in gas mixtures. This paper proposes a method to construct the ERA by coupling the decoupled single relaxation times together to a whole relaxation time. For gas mixtures with only one single relaxation process, the predicted ERA results match with the experimental data better than those predicted by the existing model. Moreover, for gas mixtures in which more than one relaxation process are significant, the ERA results predicted by the proposed method also match with the detection results of two-frequency measurements better than the existing model. This relaxation time coupling based ERA constructing method is validated by the application in low-quality natural gas detection.     

Effective Kratzer and Coulomb potentials as limit cases of a multiparameter exponential-type potential

We show that the effective Kratzer and Coulomb potentials can be obtained by taking particular limits of a multiparameter exponential potential that was studied recently. Moreover, we demonstrate that the bound state solutions of the exponential potential reduce correctly to their well-known counterparts associated with the Kratzer and Coulomb potentials. As a byproduct, we obtain a new limit relation for the hypergeometric function.     

Effective medium representation and complex modes in 3D periodic metamaterials made of cubic resonators with large permittivity at mid-infrared frequencies

We review some of the techniques that lead to the effective medium representation of a three-dimensional (3D) periodic metamaterial. We consider a 3D lattice of lead telluride cubic resonators at mid-infrared (MIR) frequencies. Each cubic resonator is modeled with both an electric and a magnetic dipole, through a method called the dual dipole approximation. The electric and magnetic polarizabilities of a cubic resonator are computed via full-wave simulations by mapping the resonator's scattered field under electric/magnetic excitation only to the field radiated by an equivalent electric/magnetic dipole. We then analyze the allowed modes in the lattice, with transverse polarization and complex wavenumber, highlighting the attenuation that each mode experiences after one free space wavelength. We observe the presence of two modes with low attenuation constant, dominant in different frequency ranges, able to propagate inside the lattice: this allows the treatment of the metamaterial as a homogeneous material with effective parameters, evaluated by using various techniques. We then show that the metamaterial under analysis allows for the generation of artificial magnetism (i.e., relative effective permeability different than unity, including negative permeability with low losses) at MIR frequencies.     

Higgs–Dilaton cosmology: Are there extra relativistic species?

Recent analyses of cosmological data suggest the presence of an extra relativistic component beyond the Standard Model content. The Higgs–Dilaton cosmological model predicts the existence of a massless particle – the dilaton – associated with the spontaneous symmetry breaking of scale invariance and undetectable by any accelerator experiment. Its ultrarelativistic character makes it a suitable candidate for contributing to the effective number of light degrees of freedom in the Universe. In this Letter we analyze the dilaton production at the (p)reheating stage right after inflation and conclude that no extra relativistic degrees of freedom beyond those already present in the Standard Model are expected within the simplest Higgs–Dilaton scenario. The elusive dilaton remains thus essentially undetectable by any particle physics experiment or cosmological observation.