Vibrational analysis of free and hydrogen bonded complexes of nicotinamide and picolinamide

Harmonic and anharmonic vibrations of free nicotinamide (NIA) and picolinamide (PIA) molecules together with their hydrogen bonded complexes H₂O–NIA and H₂O–PIA have been studied by means of density functional method. The calculation results of the vibrational spectra of free molecules have been investigated and are compared to the available experimental spectra. The vibrational wavenumbers of both molecules have also been calculated by polarizable continuum model (PCM) that represents the solvent as a polarizable continuum and places the solute in a cavity within the solvent (water is chosen as the solvent in this study). The results of PCM calculations and the H₂O–NIA, H₂O–PIA complexes, are used to investigate the H-bonding interactions of both molecules with the water molecule. The harmonic wavenumbers have been scaled by proper factors obtained by comparing the observed versus calculated wavenumbers and it is shown that anharmonic corrections on the vibrational spectra provided a better agreement between the observed and calculated wavenumbers compared to the results obtained by scaling factor method.     

Raman scattering study of the geometrically frustrated pyrochlore Y2Ru2O7

Geometrically frustrated pyrochlore Y₂Ru₂O₇, which shows a spin-glass-like transition at T_G ∼ 80 K, were investigated by temperature-dependent Raman scattering. Three discernable phonons appear around 315, 410, and 510 cm⁻¹ without any abrupt change in the number of Raman active modes within the temperature range of 10–300 K. Fitting each phonon with Lorentz oscillators, we analyzed the effects of temperature on the phonon frequencies and the linewidths. The temperature-dependence of the mode near 510 cm⁻¹ shows abnormal behavior below T_G, while the other two phonons follow the usual thermal effect of lattice vibration. This behavior can be understood in terms of spin–phonon coupling. Considering the atomic modulations of each phonon mode, it is conjectured that the 510 cm⁻¹ phonon mode is isotropically coupled to the spin degree of freedom, while the other modes are not.     

Structure of the ring in drop coating deposited proteins and its implication for Raman spectroscopy of biomolecules

Drop coating deposition Raman spectroscopy represents a new technique that enables nondestructive measurements of solutions with concentration of biomolecules down to 1 μM. It has been demonstrated that the solution structure is preserved even after drying and Raman spectra taken from the glass-like dried deposit and a solution are virtually identical. Here, we report for the first time measurements of the structure of a drop coating ring. Proteins deposited at the outer part of the ring perimeter are affected by desiccation and the spectra differ significantly from those taken in solution. Reproducible measurements of biomolecules by means of drop coating deposition Raman spectroscopy must therefore be obtained from central or slightly inward-located parts of the coating ring. The structure as well as mechanisms participating in the formation of the coating rings is explained on the basis of recently published physical theories of droplets desiccation. Formation of the final shape of the ring is analogous to processes that give rise to desiccated droplets, whereas the coating ring behaves as an “independent ring droplet” in final stages of desiccation of an ancestral droplet. Its structure is dominated by a dip or plateau in the upper part. Oscillation of the ancestral droplet contact line is probably responsible for complete desiccation of the proteins at the outer perimeter of the coating ring. It seems plausible the arrangement of a glassy “skin” at the coating ring surface caused by the accumulation of the biomolecules near this region plays an important role in preservation of “solution-like” spectral shape.     

Chemical bonding and elastic properties of Ti3AC2 phases (A = Si,Ge, and Sn): A first-principle study

The chemical bonding and elastic properties as well as the effect of atomic radii for A element in the Ti₃AC₂ phases (A = Si, Ge, and Sn) were studied by ab initio total energy calculations using plane-wave pseudopotential method based on DFT. The atomic radii of A element has a weak effect on the electronic structure. However, the bond stiffness was quantitatively examined, which shows that the bond stiffness is affected by the atomic radii of A element. The calculated results including lattice constants, internal coordinate, elastic modulus, sound velocity, and Debye temperature agree with experimental values very well. With the increase of atomic radii of A element from Si, Ge to Sn, the cohesive energy and elastic moduli as well as Debye temperature decrease, but the elastic anisotropy increases. This is related to the change of bond stiffness. It can be predicted that the fracture toughness of Ti₃SnC₂ would be comparable with that of Ti₃SiC₂ and Ti₃GeC₂.     

Growth and spectroscopic characterization of Zr:Fe:LiNbO3 crystals with various Li/Nb ratios

In this paper, Zr:Fe:LiNbO₃ crystals with various Li/Nb ratios were grown by the Czochralski method from melts having compositions varying between 48.6 and 58 mol% Li₂O. X-ray powder diffraction (XRD), inductively coupled plasma optical emission/mass spectrometry (ICP-OE/MS), ultraviolet–visible (UV–vis) absorption and the infrared (IR) spectrum were measured and are discussed in terms of the spectroscopic characterization. It was found that as the Li/Nb ratio increases in the melt, the Li/Nb ratio in the crystal also increases, the distribution coefficients of Fe and Zr ions decrease, the absorption edge shifts to a shorter wavelength, and the ZrO₂ threshold concentration of the samples decreases.     

Nonlinear perturbations of nonuniform exponential dichotomy on measure chains

This paper focuses on nonlinear perturbations of flows in Banach spaces, corresponding to a nonautonomous dynamical system on measure chains admitting a nonuniform exponential dichotomy. We first define the nonuniform exponential dichotomy of linear nonuniformly hyperbolic systems on measure chains, then establish a new version of the Grobman-Hartman theorem for nonuniformly hyperbolic dynamics on measure chains with the help of nonuniform exponential dichotomies. Moreover, we also construct stable invariant manifolds for sufficiently small nonlinear perturbations of a nonuniform exponential dichotomy. In particular, it is shown that the stable invariant manifolds are Lipschitz in the initial values provided that the nonlinear perturbation is a sufficiently small Lipschitz perturbation.     

Compactness and essential norms of composition operators on Orlicz–Lorentz spaces

In this work, we present necessary and sufficient conditions for compactness of the composition operator on Orlicz–Lorentz spaces and determine upper and lower estimates for the essential norm of the composition operator on these spaces.     

Routes to chaos in continuous mechanical systems: Part 2. Modelling transitions from regular to chaotic dynamics

In second part of the paper both classical and novel scenarios of transition from regular to chaotic dynamics of dissipative continuous mechanical systems are studied. A detailed analysis allowed us to detect the already known classical scenarios of transition from periodic to chaotic dynamics, and in particular the Feigenbaum scenario. The Feigenbaum constant was computed for all continuous mechanical objects studied in the first part of the paper. In addition, we illustrate and discuss different and novel scenarios of transition of the analysed systems from regular to chaotic dynamics, and we show that the type of scenario depends essentially on excitation parameters.     

改进的微分-差分特征列方法

基于高小山,J.Van der Hoeven等人2009年提出的微分-差分(DD)特征列方法理论,针对微分-差分系统的一些特性,在原有理论方法的基础上进行改进与补充,对升列,导元,约化等概念重新定义.提出了一则新算法(Seesaw),用来对多项式系统中的变量的类重新确定,目的是为在比较升列序的过程中重新对变量排序,在实际计算中可以降低系统求解的难度.另外对DD-伪余算法也进行了改进.