基于Weiss分子场理论对极性液体中静态介电常数随温度变化及其相应取向关联的研究

迄今为止,并没有被普遍接受的液体静态介电常数的微观理论模型, 主要原因是对属于强关联系统的液体中分子之间的取向关联特征仍不十分清楚. 本文基于Weiss分子场理论(WMFT), 对水(water, H₂O)、甲醇(methanol, CH₄O)、乙醇(ethanol, C₂H₆O)和正丙醇(1-propanol, C₃H₈O)等4种极性液体中静态介电常数, 具体为Curie-Weiss常数、Curie温度和Weiss分子场因子随温度变化规律进行分析研究, 得出上述液体中: 1)铁电关联(ferroelectric correlation, FC)和反铁电关联(anti-ferroelectric correlation, AFC)共存, 且FC比AFC强得多, 以及随温度降低FC减弱和/或AFC增强; 2)结构均匀的WMFT不能定量描述上述液体中足够低的温度下反常大的静态介电常数. 可以想象FC和较弱AFC的共存必然导致极性液体中关联序的空间不均匀, 由此作者提出了空间不均匀关联序的粗粒近似的Weiss分子场理论, 并用此理论对上述液体中静态介电常数随温度快速变化的行为进行了解释. 上述结果对深入认知液体物理学, 包括玻璃化转变机制的探索, 无疑是有价值的.     

用Weiss分子场理论对有外电场时铁电体系相变特征的研究

Weiss分子场理论(WMFT)对晶体中顺磁-铁磁和顺电-铁电相变特征的定量描述是相当成功的. 由于是平均场理论,又可作为初步分析结构无序体系和复杂组分体系相变行为的理论依据. 但是迄今为止,并没有对有外场时WMFT的相变特征进行详细研究. 而对铁电体系,仅仅对分子取向为两个状态时WMFT的相变特征进行了研究. 另外,虽然铁磁与铁电体系的WMFT描述极为相似,但是由于两种体系中微观磁化和极化的单元不同,导致相应的数学描述与结果也有所不同. 本文首先对外电场中分子取向包含任意状态的铁电体系的WMFT相变特征, 包括自发极化、内能和比热以及静态极化率随温度变化进行严格推导, 然后对相变特征随外电场的演变进行了研究.结果表明: 1)无外场时,体系发生二级顺电-铁电相变,且随状态数的增加,相变温度减小, 这是与铁磁体系不同的地方,同时单分子的平均极化强度减小,而内能、比热和极化率增大; 2)外场的存在,使得体系原有的二级相变转化为弥散相变,且外场越强,弥散温区越大. 上述结果对深入研究铁电体系的相变,特别是弥散相变无疑是有益的.     

掺杂型聚合物的电晕极化特性及其机理研究

实验研究了聚甲基丙烯酸甲脂(PMMA)掺杂生色团分散红DR19的电光聚合物的电晕极化特性.结合吸收光谱法和显微镜形貌分析了极化电压、极化温度以及极化时间对极化效果的影响.理论和实验分析得出极化电压增大可以增大聚合物内部极化电场,但电压过大会引起薄膜击穿而降低极化效果;而极化温度升高可以增大分子取向力,但在聚合物玻璃化温度以上会导致相分离;极化时生色团分子的取向随时间增大并逐渐达到动态平衡.实验结果表明:表征极化效果的序参数随极化电压的增大而先增大后减小,随极化温度的升高而先增大后减小,随极化时间的增长先增大后趋于稳定.     

铁磁/半导体(绝缘体)/铁磁异质结中渡越时间与两铁磁层磁矩夹角变化的关系

在群速度概念的基础上, 研究了自旋极化电子隧穿通过铁磁体/半导体(绝缘体)/铁磁体异质结时, 渡越时间随两端铁磁层中磁矩夹角变化的关系. 研究结果表明: 当中间层为半导体层时, 由于半导体层中的Rashba自旋轨道耦合强度的影响, 自旋向上电子和自旋向下电子的渡越时间差会在两铁磁层相对磁矩夹角为π/2和3π/2附近出现一个极小值. 当中间层为绝缘体层时, 势垒高度的变化会导致不同取向的自旋极化电子渡越时间差的变化, 并当势垒高度超过一临界值时发生翻转. 关键词： 铁磁体/半导体(绝缘体)/铁磁体异质结 Rashba自旋轨道耦合强度 渡越时间 磁矩     

极化条件对偶氮化合物薄膜中分子取向的影响

 为探索不同的极化条件对分子取向的影响,用旋涂法制备了偶氮主客体掺杂薄膜,并用电晕极化的方法分别在不同温度和厚度条件下使分子取向,通过测量极化前后紫外-可见吸收谱,研究了平均取向因子的变化,并和二次谐波产生结果进行了比较。实验结果表明：对于厚度相同的偶氮薄膜,随着温度的升高,平均取向因子增大,但二次谐波信号强度先增大后减小;温度越接近聚合物玻璃转变温度,分子越容易取向,但温度过高,聚甲基丙烯酸甲酯变为粘滞态,部分偶氮分子容易在高温下蒸发掉,导致二次谐波信号强度降低,而平均取向因子增大;随着薄膜厚度的增大,针-板电极电场造成薄膜内部电场分布的不均匀性增加,极化效率降低,平均取向因子不断减小,二次谐波信号强度先增大后减小。     

静电场对SmC^＊相液晶作用的计算研究

采用自洽模拟方法,计算研究了分子层面内的静电场对ＳｍＣ＾＊相液晶螺旋结构和铁电特性的影响。结果表明,ＳｍＣ＾＊相液晶的螺距和极化强度平均值随场强增大而增大,且越接近阈值电场增大真快;指向矢倾斜角和分子取向序参量随场强增大而缓慢增大;阈值电场与液晶的本征螺距和自发极化强度有关,并随温度升高而减小。     

时域方法在铁电相变研究中的应用

提出了时域参数的概念。在(49±1)℃的小温度范围内研究了TGS单晶的铁电相变过程中时域和频域介电谱随温度的变化。分出了晶格极化、畴运动和屏蔽电荷激发三种机构提供的信息。后两种机构在此温度范围内使静态介电常数与音频介电常数之比值由接近于1突增至2.5以上。损耗峰主要是屏蔽电荷的贡献,相应自由弛豫时间在48.615℃附近出现奇异性质。 关键词：     

一维复合颗粒链中能量衰减的动力学分析

重颗粒区域由压缩到稀疏的结构转变导致了一维复合颗粒链中能量衰减的渡越行为,并且这种结构转变与界面附近重颗粒的运动状态的变化密切关联.分析表明这种运动状态的转变导致了界面处的反射率在两个分支存在较大差别,从而导致了轻颗粒区域能量在两个分支以不同的速率衰减. 关键词： 复合颗粒链 渡越     

弛豫铁电体弥散相变的玻璃化特性研究

根据弛豫铁电材料在相变区域的介电弥散行为和玻璃化 液体材料在过冷状态下黏度与温度的行为所共同满足的Vogel-Fulcher 函数关系, 分析了施主替代钛酸钡系列陶瓷的缺陷补偿原理, 通过引入玻璃化液体的构型熵概念, 研究了弛豫铁电材料中钛阳离子缺陷作用势的温度关系, 得到了如下结论: 施主掺杂含量的增加导致了无序度的增加, 钛离子缺陷浓度的增大和平均极性区域尺寸的减小; 在构型熵满足Vogel-Fulcher 函数关系的条件下, 温度越低, 钛离子缺陷作用的范围越大, 极化区域也越大. 缺陷作用的范围随温度的变化导致了弛豫铁电材料的弥散性. 温度下降到一定程度, 冻结效应发生, 介电弥散现象消失.     

液体-液体相变与反常特性

绝大多数物质的液态密度随温度降低而增大,即常见的热胀冷缩现象.但存在一类物质,如水及第四主族的硅、锗等,其液态密度在一定温度范围内随温度的升高而增大,即密度反常现象.此外,该类物质还存在动力学反常(密度越大粒子运动越快)、热力学反常(热力学量的涨落随温度降低而升高)等其他反常特性.这类材料的化学性质千差万别,但却具有相似的物理反常特性.进一步的理论研究发现部分材料具有两种液态,即高密度液态和低密度液态,两者之间存在一级相变.因此,反常特性与液体-液体相变是否有直接关联是一个值得深入研究的课题.本文主要介绍了具有液体-液体相变的一类材料及其反常特性,包括高温高压下氢的液体-液体相变及其超临界现象,镓的反常特性及其与液体-液体相变的关联等.     

A theory of electric polarisation in liquids: II. Polar liquids

In the frame of a theory previously developed by the author for non-polar liquids, the static dielectric constant of polar liquids is described through a new formula without adjustable parameters, valid for spherical molecules carrying a mathematical dipole. The application of the formula to 20 polar liquids shows that the dipole moments resulting from the theory are satisfactorily compared with those deduced from vapour phase data. The agreement obtained in this way between theory and experiment is better than that obtained through the analogous Onsager's formula.     

On the theory of dielectric relaxation

The Kirkwood expression for the static dielectric constant of a polar substance is extended to non-zero frequencies by a means which avoids the introduction of spherical specimens and the connection between the dipoledipole correlation functions of distinct spatial regions. The procedure is based on a previously derived relation between the dynamic dielectric constant and the current-current susceptibility and on the use of the Callen-Welton theorem to relate the susceptibility to fluctuations. Surface effects are eliminated at the outset by consideration of media which are infinite in extent. A general relation between the long-range dipole-dipole correlations (which fall off as the inverse cube of the distance) and short-range correlations in a specimen composed of non-polarizable molecules is found from a consistency relation. It is shown that the two microscopic relaxation times which result from the existence of but one relaxation time in the dielectric constant correspond to the transverse and longitudinal relaxation times with the longitudinal time being screened relative to the transverse time by the static dielectric constant.     

A CNDO/2 calculation on the radical formed on electron irradiation of mesitylene

Mori's method is applied to the calculation of the collective molecular orientation correlation functions which are of interest in light scattering and dielectric relaxation. The case of liquids composed of asymmetric top molecules is discussed. For the collective variables, the usual ‘rotational diffusion’ assumptions do not yield the single-particle rotational diffusion results unless there exists no orientational order in the medium. This point is discussed with regard to the results of some recent light scattering and dielectric relaxation experiments.     

A microscopic theory of a quasi-crystalline transition layer on the surface of semi-infinite liquid dielectrics upon brewster light reflection and the near-field effect

An adequate theoretical interpretation of experiments on Brewster light reflection from the surfaces of liquids is given on the basis of the near-field effect in the transition layer. The analysis is carried out in terms of the model of a discrete-continuous dielectric, which takes into account the fields of atomic (molecular) dipoles discretely distributed inside the Lorentz sphere surrounding the point of observation. The liquids under consideration that have anisotropic molecules are characterized by a diagonal polarizability tensor within the transition layer and by scalar polarizability in the bulk of the liquid. It is shown that agreement between theoretical and experimental values of the ellipticity of reflected light is obtained due to a random change within a finite interval of the angle of orientation of molecules in the lattice sites in the transition layer. This makes it possible to conclude that the transition layer in the liquids under consideration is quasi-crystalline.     

On the dynamics of liquids in their viscous regime approaching the glass transition

Recently, Mallamace et al. (Eur. Phys. J. E 34, 94 (2011)) proposed a crossover temperature, T(×), and claimed that the dynamics of many supercooled liquids follow an Arrhenius-type temperature dependence between T(×) and the glass transition temperature T(g). The opposite, namely super-Arrhenius behavior in this viscous regime, has been demonstrated repeatedly for molecular glass-former, for polymers, and for the majority of the exhaustively studied inorganic glasses of technological interest. Therefore, we subject the molecular systems of the Mallamace et al. study to a "residuals" analysis and include not only viscosity data but also the more precise data available from dielectric relaxation experiments over the same temperature range. Although many viscosity data sets are inconclusive due to their noise level, we find that Arrhenius behavior is not a general feature of viscosity in the T(g) to T(×) range. Moreover, the residuals of dielectric relaxation times with respect to an Arrhenius law clearly reveal systematic curvature consistent with super-Arrhenius behavior being an endemic feature of transport properties in this viscous regime. We also observe a common pattern of how dielectric relaxation times decouple slightly from viscosity.     

Holographic interferometry of liquids at the He-Ne laser wavelength under microwave irradiation

Changes in the optical refractive indices of a number of organic liquids, water, and some biological aqueous solutions exposed to (37.5–78)-GHz electromagnetic radiation have been investigated using a differential holographic interferometer. It is established that irradiation with intensities up to 10 mW/cm² may reduce the refractive index of liquids by ～10^?3 as a result of thermal changes in the dielectric constant of the material studied. The magnitude and dynamics of changes in the refractive index are determined by the irradiation intensity and physical parameters of liquids (dipole moment of molecules, absorption coefficient, permittivity, and temperature coefficient of the refractive index) and are independent (within the experimental error) of the mutual orientation of the polarization unit vectors of the microwave and optical fields.     

A theory of electric polarisation in liquids : I. Nonpolar liquids

The static dielectric constant of nonpolar liquids is described by analyzing the pair distribution function and the dipole-dipole interaction into a finite set of Fourier components. In a mean field approximation the theory leads to a final formula that does not contain any adjustable parameter, and proves to work better than the Clausius-Mossotti equation. The theory explains in a satisfactory way the temperature and pressure dependence of the dielectric constant of nonpolar liquids, as well as the temperature variation of the refractive index of many organic polar liquids.     

Dielectric absorption in mixtures of anisole with some primary alcohols at microwave frequency

Dielectric properties of binary mixtures of anisole with methanol (MeOH), 1-propanol (1-PrOH), 1-butanol (1-BuOH) and 1-heptanol (1-HeOH) over an entire concentration range have been studied at a fixed temperature 40°C. The dielectric constant (ε′) and dielectric loss (ε″) of the binary mixtures of polar liquids have been determined at a microwave frequency of 9.1?GHz. The static dielectric permittivity (ε ₀) of the liquid samples was also determined using a precision LCR meter. Determined values of static dielectric permittivity (ε ₀) and dielectric permittivity (ε*) at 9.1?GHz frequency were used to evaluate relaxation time (τ) and high frequency limit dielectric permittivity (ε _∞). Dielectric parameters were interpreted in terms of molecular interaction between the anisole and alcohol molecules.     

Testing “microscopic” theories of glass-forming liquids

We assess the validity of “microscopic” approaches of glass-forming liquids based on the sole knowledge of the static pair density correlations. To do so, we apply them to a benchmark provided by two liquid models that share very similar static pair density correlation functions while displaying distinct temperature evolutions of their relaxation times. We find that the approaches are unsuccessful in describing the difference in the dynamical behavior of the two models. Our study is not exhaustive, and we have not tested the effect of adding corrections by including, for instance, three-body density correlations. Yet, our results appear strong enough to challenge the claim that the slowdown of relaxation in glass-forming liquids, for which it is well established that the changes of the static structure factor with temperature are small, can be explained by “microscopic” approaches only requiring the static pair density correlations as nontrivial input.