Microphase separation at two length scales

The possibility of microphase separation at two different length scales in monodisperse AB block copolymer melts consisting of a homopolymer A block and either a linear alternating AB copolymer block (poly(A)_m-block-poly(B-alt -A)_n) or an AB comb copolymer block poly(A)_m-block-poly(A-graft-B)_n, is investigated. An analysis of the structure factor reveals that in the parameter space of n and m three different cases can be distinguished: I) The structure factor has only one minimum corresponding to the short length scale (i.e. the characteristic length of the repeating unit of the alternating or comb block). II) The structure factor has only one minimum corresponding to the long length scale (the characteristic length of the blocks). III) Two minima are present leading to a competition between microphase separation at the short and the long length scale. Depending on the choice of n and m, one of these three possibilities will occur. Received 25 August 2000     

氦对LaNi5晶体结构的影响及其扩散特性研究

从密度泛函理论为基础的第一性原理出发,运用全势能线性缀加平面波(FLAPW)方法,对氚衰变后氦在合金中的占位以及LaNi₅He晶体结构进行了理论计算,并系统给出了氦在间隙间的迁移曲线.结果表明,氦原子在十二面体(1b)格位最稳定,并且氦从6m格位向1b格位迁移不存在势垒,而从2d格位向1b格位迁移则需越过1.55eV高的势垒.另外,氦从12n格位穿过12o格位最后到达6m格位也无明显势垒存在,并且处于4h格位之间的氦原子可以自由迁移,而相应12n格位之间的直接迁移则需跨越13.6eV高的势垒.最后还计算给出了氚衰变后合金的态密度、电子密度以及势能分布图,并与相应的LaNi₅H结构作了详细比较. 关键词： 全势能线性缀加平面波(FLAPW) 5He')" href="#">LaNi₅He 态密度 扩散     

Non-partial-wave Coulomb-Born theory for the excitation of many-electron atomic ions II: Numerical description and application

A non-partial-wave Coulomb-Born theory is recently formulated to treat the excitation of many-electron atomic ions for impact by an arbitrary charged particle [Y.B. Duan et al., Phys. Rev. A 56, 2431 (1997)]. The multiple expansion of the transition matrix element is decomposed into the target form factor and the projectile form factor. These are the matrix elements of the tensor operators between quantum states so that any complicated wave function for the target ion can be employed. In this formal theory, an infinitesimally small positive quantity is introduced artificially to guarantee the convergence of integrals. As a supplementary part of the theory, we discuss how to choose the value of . It is found that the should be taken as functions of the momentum transfer and multipolarity . Illustrations are carried out by calculating the cross-sections for some typical transitions n _a l _a -n _b l _b of hydrogen-like ions for impact by electron, positron, and proton, respectively. The resulting cross-sections are in good agreement with ones produced by using a method available for ion targets with Slater-type orbitals [N.C. Deb, N.C. Sil, Phys. Rev. A 28, 2806 (1993)]. Comparisons demonstrate that the Coulomb-Born theory with non-partial wave analysis provides a powerful method to treat the excitation of many-electron atomic ions impact by an arbitrary charged particle. Received 6 April 1999     

Exact Solution for a Class of Random Walk on the Hypercube

A class of families of Markov chains defined on the vertices of the n-dimensional hypercube, Ω _n ={0,1} ⁿ , is studied. The single-step transition probabilities P _n,ij , with i,j∈Ω _n , are given by P_n,ij=\frac(1-a)^d_ij(2-a)ⁿP_{n,ij}=\frac{(1-{\alpha})^{d_{ij}}}{(2-{\alpha})^{n}}, where α∈(0,1) and d _ij is the Hamming distance between i and j. This corresponds to flip independently each component of the vertex with probability \frac1-a2-a\frac{1-{\alpha}}{2-{\alpha}}. The m-step transition matrix P_n,ij^mP_{n,ij}^{m} is explicitly computed in a close form. The class is proved to exhibit cutoff. A model-independent result about the vanishing of the first m terms of the expansion in α of P_n,ij^mP_{n,ij}^{m} is also proved.     

Orientational order parameter studies on 3.Om and 3O.Om liquid crystals

Orientational order parameter S is evaluated in the nematic phase of six liquid crystal compounds, N-(p-n-propyl benzylidene)-p-n-alkoxy anilines, 3.Om and N-(p-n-propyloxy benzylidene)-p-n-alkoxy anilines, 3O.Om compounds with m = 6, 7 and 8, using different methods. The techniques employed are S from birefringence δn, Haller's approximation from (1?T/T_c) ^β, effective geometry parameter α_g and Vuks’ scaling factor S_C. The values of S obtained using the above methods are compared with one another and with the results on a number of liquid crystals; the liquid crystals favor isotropic Vuks’ method.     

Crystallization in Microdomains of a Block Copolymer Comprising Semicrystalline Block Observed by Simultaneous Measurement of SAXS and WAXS with H v‐SALS or DSC

Abstract

Semicrystalline block copolymers provide us with a fascinating model for studying the kinetics of crystallization. We performed the simultaneous measurement of small‐ (SAXS) and wide‐angle (WAXS) x‐ray scattering (SWAXS) with differential scanning calorimetry (DSC), or SWAXS with small‐angle light scattering (H _v‐SALS). The specimen used was polyethylene‐b‐poly(ethylene propylene) (PE‐b‐PEP) with the molecular weight of 44,200. The PE block has the melting point (T _m) at 108°C. We observed the time evolution of crystallization in the lamellar microdomains of PE‐b‐PEP after a temperature drop from 180°C (?T _m) to a variety of temperatures slightly below T _m. The exothermic signal was observed by DSC right after the temperature drop, while the four‐leaf‐clover pattern of H _v‐SALS and the SAXS peaks due to the lamellar microdomains were observed several minutes after the temperature equilibration. The WAXS peaks of (110) and (200) reflection were almost simultaneously detected with the H _v‐SALS and the SAXS peaks at crystallization temperature of 100°C. With the crystallization temperature closer to T _m, the WAXS crystalline signals showed up with longer time lag after the H _v‐SALS and the SAXS peaks began to appear. Interestingly, these phenomena are interpreted as that long‐range order of density fluctuation up to the order of micrometers was generated prior to the formation of crystals with partially ordered phase rather than the instantaneous crystalline nucleation.     

Mesostructures and properties of transparent block copolymer/silica nanocomposite monoliths

In this work, three different block copolymer/silica hybrid nanocomposite monoliths that possess mesostructured domains (hexagonal, cubic, and disordered) were prepared through the micellization of the block copolymer during the sol-gel process of a silica precursor. Transparent block copolymer/silica nanocomposite monoliths were obtained from the amphiphilic triblock copolymer poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (EO₁₀₆PO₇₀EO₁₀₆, Pluronic F127), which we used to organize the polymerizing silica networks; the ratio between the block copolymer and silica was fixed at 60:40 (wt%). Small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) were used to observe the mesostructural ordering. Temperature-dependent SAXS patterns of the cubic structured nanocomposites showed that the calcination process takes place at 210°C. The transmittances of the nanocomposite monoliths over the range of wavelengths from 400 to 800 nm was >85%. From rheological measurements at low frequency, it was found that the hexagonally structured monoliths had higher storage and loss moduli relative to the monoliths possessing cubic and disordered structures.     

SimCn （m+n≤7）团簇的密度泛函研究

使用密度泛函理论（DFT）的杂化密度泛函B3LYP方法在6-31G*基组水平上对Si_mC_n（m+n≤7）团簇各种可能的构型进行几何结构优化,预测了各团簇的最稳定结构. 并对最稳定结构的平均结合能（E_b）,二阶能量差分（Δ₂E）和能隙（E_g）等进行了理论研究. 结果表明,随着原子个数的增加,SiC二元团 关键词： mC_n （m+n≤7）团簇')" href="#">Si_mC_n （m+n≤7）团簇 密度泛函理论 结构与性质     

Evaluation of Effective Resistances in Pseudo-Distance-Regular Resistor Networks

The effective resistance or two-point resistance between two nodes of a resistor network is the potential difference that appears across them when a unit current source is applied between the nodes as terminals. This concept arises in problems which deal with graphs as electrical networks including random walks, distributed detection and estimation, sensor networks, distributed clock synchronization, collaborative filtering, clustering algorithms and etc. In the previous paper (Jafarizadeh et al. in J. Math. Phys. 50:023302, 2009) a recursive formula for evaluation of effective resistances on the so-called distance-regular networks was given based on the Christoffel-Darboux identity. In this paper, we consider more general networks called pseudo-distance-regular networks or QD type networks, where we use the stratification of these networks and show that the effective resistances between a given node, say α, and all of the nodes β belonging to the same stratum with respect to α, are the same. Then, based on the spectral techniques, for those α,β’s which satisfy L^-1_aa=L^-1_bbL^{-1}_{\alpha\alpha}=L^{-1}_{\beta\beta} (L ⁻¹ is the pseudo-inverse of the Laplacian of the network), an analytical formula for effective resistances R_ab^(m)R_{\alpha\beta^{(m)}} (the equivalent resistance between terminals α and β, so that β belongs to the m-th stratum with respect to α) is given in terms of the first and second orthogonal polynomials associated with the network. From the fact that in distance-regular networks, L^-1_aa=L^-1_bbL^{-1}_{\alpha\alpha}=L^{-1}_{\beta\beta} is satisfied for all nodes α,β of the network, the effective resistances R_ab^(m)R_{\alpha\beta^{(m)}} for m=1,2,…,d (d is diameter of the network which is the same as the number of strata) are calculated directly, by using the given formula.     

Maleic Acid–alt–Styrene Copolymer as Compatibilizer for Poly(Ethylene Oxide)-Poly(Styrene)Blends

Maleic acid-alt-styrene (MAaS) copolymer with number-average molecular weight [Mbar] _n = 2500 was used as a compatibilizer in blends of poly(ethylene oxide) (PEO) and poly(styrene) (PS). PEO with weight-average molecular weight [Mbar] _w = 10⁵ (PEO₁₀₀) and two PS samples with [Mbar] _w = 9 × 10⁴ and 4 × 10⁵, respectively (PS₉₀ and PS₄₀₀, respectively) were used. A depression of the melting temperature T _m of PEO in blends containing MAaS relative to pure PEO and PEO/PS blends was observed. The melting enthalpy ΔH _m for the PEO/PS blends containing MAaS was lower than those of pure PEO and PEO/PS blends without compatibilizer. The crystallization kinetics of PEO and the blends were studied by differential scanning calorimetry (DSC) at different crystallization temperatures T _c. Flory-Huggins interaction parameters χ₁₂ for the blends were estimated. Their values are in good agreement with those obtained for similar systems and suggest that the free energy of mixing ΔG _mix should be negative. Polarized optical microscopy shows differences in the macroscopic homogeneity of the blends containing compatibilizer that could be attributed to a compatibilization process.     

杂双子咪唑表面活性剂的合成及其表面性能

合成了一系列以两个亚甲基为联接基的杂双子咪唑表面活性剂([C_m-2-C_nim]Br_{2, m, n}=8, 10, 12, 14, 16; m≠n). 用氢谱和质谱对其结构进行了表征. 探索了物料比、反应温度和时间对反应产率的影响. 对合成的杂双子咪唑表面活性剂的表面活性进行了研究,讨论了分子结构的不对称程度对表面活性的影响.     

Phase transitions in liquid crystal 6O.4 (p-<Emphasis Type="Italic">n</Emphasis>-hexyloxybenzylidine-p′-<Emphasis Type="Italic">n</Emphasis>-butylaniline)

DSC measurements on p-n-hexyloxybenzylidine-p′-n-butylaniline (6O.4) showed that the crystalline to liquid crystalline (K-S _H) transition at 33.7°C observed in the heating cycle does not revert even when the sample is cooled down to −100°C. Hence it is inferred that a physically stable supercooled liquid crystalline phase is formed on cooling 6O.4. To investigate the K-S _H transition further the techniques of polarized microscopy and X-ray diffraction were used which concurred with the DSC results. Quasielastic neutron scattering measurements carried out to study the re-orientational motions in the ordered phases of 6O.4 (K and S _H) show that while in the crystalline phase (at RT) the re-orientational motion is found to involve only the core of the molecule, in the S _H phase (at 45°C) the dynamics involves the whole molecule and this motion is found to persist even when the sample cools back to room temperature corroborating the results of the DSC, microscopy and X-ray diffraction.      

Resonance optical spectroscopy of long-period quantum-well structures

Theory of specular light reflection from long-period quantum-well structures taking into account the exciton contribution to dielectric polarization has been developed for an arbitrary relation between the background refractive index in the well, n _a, and barrier-material refractive index nb. General expressions for the optical reflection and transmission coefficients for a structure with N equidistant quantum wells are derived with the use of the Green’s function and transfer matrix methods. Normal and oblique light reflectance spectra from II-VI-based heterostructures were found to reveal a bright interference pattern caused by the difference between n _a and n _b. A comparison of the theory with experiment has yielded the dispersion of n _a and n _b within a broad wavelength range and the parameters of the quasi-two-dimensional heavyhole exciton (e1-hh1), namely, the resonant frequency and the radiative and nonradiative damping rates. Reflectance spectra from resonant Bragg and quasi-Bragg structures with real exciton parameters are calculated, and the effect on these spectra of the refractive-index difference and the deviation from the Bragg condition is analyzed. Fiz. Tverd. Tela (St. Petersburg) 39, 2072–2078 (November 1997)     

Temperature dependence of the dual phosphorescence from xanthone in n-hexane matrices

The phosphoresence spectrum and lifetime of xanthone embedded in an n-hexane matrix has been investigated as a function of temperature (1·6-100 K). Vibrational analyses of the spectra reveal that emission occurs from three sites, two of which are dominant. Emission from one site (B) occurs from the ³ nπ* state of a planar xanthone molecule and is characterized by strong totally symmetric carbonyl stretching vibrations and a short lifetime (2·4 ms). Emission from the other site (C) is shown to arise from the ³ππ* state of an out-of-plane distorted xanthone molecule. It displays a vibrational structure rich in modes of a ₁, b ₁, and b ₂ (C _2v notation) symmetry and a long lifetime (115 ms). Both direct spin orbit coupling via configurational mixing of the nπ* and ππ* states due to the non-planarity of the molecule in its ³ππ* state and spin-orbit vibronic interaction involving ³ A ₁(ππ*)-¹ A ₂(nπ*) spin-orbit and ¹ A ₂(nπ*)-¹ B ₂(ππ*) vibronic interaction via out-of-plane b ₁ vibrations are shown to be responsible for the C site emission intensity. Vibronic mixing between the ³ππ* and ³ nπ* states is not important. With increasing temperature, the phosphorescence intensity from the B site (³ nπ*) emitters increases at first, reaches a maximum at ～20 K and then decreases. The C site (³ππ*) intensity simply decreases with rising temperature. At a given temperature, the phosphorescence lifetimes are identical and exponential for all emission bands regardless of site origin. These observations indicate an equilibrium between emitters in the two sites throughout the lattice. A phonon-assisted energy transfer mechanism is proposed to account for these observations.     

Stilbene-Like Molecules as Fluorescent Probes Applied for Monitoring of Polymerization Process

2-(p-N,N-dimethylaminostyryl)benzoxazole (OS), 2-(p-N,N-dimethylaminostyryl)-benzothiazole (SS) and 2-(p-N,N-dimethylaminostyryl)naphtiazole (PS) were prepared and their absorption and fluorescence spectra were measured in various solvents at room temperature. On the basis of the solvatochromic behavior the ground state (μ_g) and excited state (μ_e) dipole moments of these pN,N-dimethylaminostyryl derivatives were evaluated. The dipole moments (μ_g and μ_e) were estimated from solvatochromic shifts of absorption and fluorescence spectra as function of the dielectric constant (ɛ) and refractive index (n) of applied solvents. The absorption spectra only slightly are affected by the solvent polarity in contrast to the fluorescence spectra that are highly solvatochromic and display a large Stokes shift. The analysis of the solvatochromic behavior of the fluorescence spectra as function of Δf (ɛ, n) revealed that the emission occurs from a high polarity excited state. The large dipole moment change along with the strongly red-shifted fluorescence, as the solvent polarity is increased, demonstrate the formation of an intramolecular charge transfer state (ICT). Compounds under the study were used as fluorescence probes for monitoring the kinetics of polymerization. The study on the changes in fluorescence intensity and spectroscopic shifts of studied compounds were carried out during thermally initiated polymerization of methyl methacrylate (MMA) and during photoinitiated polymerization of 2-ethyl-2-(hydroxymethyl)propane-1,3-diol triacrylate (TMPTA).     

Probing the structural,bonding, electronic and magnetic properties of transition–metal borazine systems: Co m (borazine) n (m = 1, 2; n = 1–3)

ABSTRACT

The geometrical structures of neutral and anionic Co _m (borazine) _n (m?=?1, 2; n?=?1–3) complexes have been determined by using density functional theory. The results indicate that most of the ground state structures for the complexes are similar to those of Co _m (benzene) _n , which might because borazine is isoelectronic and isostructural to benzene. The frontier molecular orbitals (FMOs) analyses show that their FMOs mainly arise from the 3d/4s electrons of cobalt atoms and the weak π-cloud of borazine molecule. Furthermore, the magnetic moments of complexes were studied and the results revealed that the Co atoms carry most of the magnetic moments. Comparing with the magnetic moment of a free Co atom (3.0μ_B), the magnetic moments of Co atom in most of Co _m (borazine) _n ^0/- complexes are significantly reduced and even quenched except that the Co(borazine) remains unchanged. More importantly, there is a transition FM-to-AFM between neutral and anionic Co₂(borazine)₂. Finally, natural population analyses were performed to insightfully explore the reliable electronic structure properties.     

Odd-even effect of the number of free valence electrons on the electronic structure properties of gold-thiolate clusters

ABSTRACT

It is essential to understand the intrinsic stability of the gold-thiolate clusters, which present extensive potential applications in many fields such as the catalysis, biomedicines and molecular machines. The electronic structures and aromaticity indexes of a series of Au_m(SH)_n (m, n?=?5–12) were comprehensively investigated through energetic, vibrational, magnetic, and electronic density properties, which are highly sensitive to the size and topological structure of the cluster. Generally, computational results of energy gap between the frontier molecular orbitals, normalized atomization energy (NAE), and electron localization function (ELF)-σ values exhibit the odd-even effect, in which clusters with the even number of free valence electrons, being reflected by the value of (m–n), possess relatively higher stability than the odd one. However, it is difficult to describe the stability of cluster with the sophisticated three-dimensional structure through one single aromaticity index such as the nucleus-independent chemical shift (NICS) value. Principal component analysis and clustering analysis of the calculation results of Au_m(SR)_n clusters suggest that the value of (m–n) and the Au₄ unit are important for predicting the stability of the Au clusters.     

The flexoelectric effect in nematic liquid crystals: A statistical- mechanical approach

The flexoelectric coefficients e₁ and e₃ for polar liquid crystals, such as 4-n-pentyl- 4^′-cyanobiphenyl, are investigated theoretically by means of an integral equation approach, which takes into account translational, orientational correlations as well as their coupling. e₁ and e₃ are evaluated from microscopic expressions derived on the basis of a density-functional method. Received 27 April 2001 and Received in final form 27 August 2001     

过渡族元素掺杂BaTiO3-Tb1-xDyxFe2-y层状复合材料中的磁电效应

用溶胶-凝胶法制备1.0%mol Mn,Cr,Co掺杂 BaTiO₃(BTO)粉体,在1350℃下烧结成多晶陶瓷样品.X射线衍射和差示扫描量热分析表明,室温下掺杂BaTiO₃具有四方钙钛矿结构;居里点和相变潜热随Cr,Mn,Co掺杂逐渐降低.将掺杂BaTiO₃与Tb_1-xDy_xFe_2-y(TDF)胶合制成双层磁电复合材料,并研究了Cr:BTO-TDF,Mn∶BTO-TDF,Co:BTO-TDF层状复合材料中的磁电效应.实验表明,在340×80 A·m^-1偏置磁场下, Cr:BTO-TDF的横向磁电电压系数达到最大值586 mV·cm^-1·(80 A·m^-1)^-1.在400×80 A·m^-1偏置磁场下,Mn∶BTO-TDF和Co:BTO-TDF的横向磁电电压系数的最大值分别为480 mV·cm^-1·(80 A·m^-1)^-1和445mV·cm^-1·(80 A·m^-1)^-1.研究表明掺杂BaTiO₃-TDF层状复合材料中具有较强的磁电耦合.作为无铅压电材料,掺杂BaTiO₃制备的磁电效应器件颇具应用前景. 关键词： 磁电效应 双层复合材料 3')" href="#">掺杂BaTiO₃ 1-xDy_xFe_2-y')" href="#">Tb_1-xDy_xFe_2-y     

Vibrational spectroscopy of the seselin crystal

Seselin, C₁₄H₁₂O₃, is a coumarin which crystallizes in a monoclinic structure P2₁/b(C_2h⁵) with four molecules per unit cell. In a Fourier‐transform Raman spectroscopic study performed at room temperature, several normal modes were observed. Vibrational wavenumber and wave vector calculations using density functional theory were compared with experiment, which allowed the assignment of a number of normal modes of the crystal. Temperature‐dependent Raman spectra were recorded between 10 and 300 K. No anomalies were observed in the phonon spectra, indicating that the monoclinic structure remains stable. Copyright © 2007 John Wiley & Sons, Ltd.