Temperature dependence of ratio between dielectric anisotropy and order parameter in fluorinated nematic liquid crystals

Temperature dependence of ratio between dielectric anisotropy and order parameter of fluorinated nematic liquid crystal is investigated by using a semi-empirical molecular orbital package that can accurately calculate an angle between molecular dipole moment and long axis. We optimize the molecular conformations with three semi-empirical Hamiltonians AM1, PM3 and PM5, and then make a comparison between computational results and experimental measurements. It is shown that the results obtained from AM1 method are in good agreement with the measurements. The present study offers an applicable method to predict the dielectric properties of liquid crystal material.     

双氟取代苯和联苯类液晶化合物的量子化学研究

运用AM1和PM3两种SCF-MO方法,通过能量梯度全优化计算,给出了对一系列环上双氟取代苯、联苯液晶化合物的稳定几何构型、电子结构和分子基本性质(生成热、偶极矩、前沿分子轨道能级等)。联系有机结构理论进行了分析和讨论。初步阐明了其分子结构与介电各向异性之间的关系,为设计和开发新型液晶分子研究提供了有较大价值的线索。     

环上双氟取代三联苯类液晶化合物的量子化学研究

运用AM1和PM3两种SCF-MO方法,通过能量梯度全优化计算,给出了对环上双氟取代三联苯类液晶化合物的稳定几何构型、电子结构和生成热、偶极矩、前线分子轨道能级等分子的基本性质.联系有机结构理论进行了分析和讨论.初步阐明了其分子结构与介电各向异性之间的关系,为设计和开发新型液晶分子提供了有较大价值的线索.     

Calculating the dielectric anisotropy of nematic liquid crystals: a reinvestigation of the Maier——Meier theory

This paper investigates the average dielectric permittivity (\overline ε ) in the Maier--Meier theory for calculating the dielectric anisotropy (Δε) of nematic liquid crystals. For the reason that \overline ε of nematics has the same expression as the dielectric permittivity of the isotropic state, the Onsager equation for isotropic dielectric was used to calculate it. The computed \overline ε shows reasonable agreement with the results of the numerical methods used in the literature. Molecular parameters, such as the polarizability and its anisotropy, the dipole moment and its angle with the molecular long axis, were taken from semi-empirical quantum chemistry (MOCPAC/AM1) modeling. The calculated values of Δε according to the Maier--Meier equation are in good agreement with the experimental results for the investigated compounds having different core structures and polar substituents.     

Investigation of aminotrimethoxysilanes and organic acids functionalized surface interactions: Theoretical and atomic force microscopy studies

Silane compounds provide many applications in biotechnology field. Chemically adsorbed silanes with reactive terminal groups are used for fabrication of functional material, which can serve as a model substrate for fundamental studies of different surface interactions or as a platform for further chemical reactions.In this work, silane compounds with amine groups were the area of interest. The studies were focused on investigation of amine group interaction with different acid groups. The interactions were probed using atomic force microscope operating in force spectroscopy mode. An atomic force microscope gold tip, functionalized with thiol compounds, served as acid-terminated surface. Interactions at interfaces between the silane self-assembled monolayer (SAM) and the thiol SAM were measured in liquid environment. The results of the measurements were set against the theoretical studies performed by AM1d and PM5 semi-empirical methods. Moreover, prior to chemical force spectroscopy measurements the silane films coverage quality was studied as well. Fourier transform infrared (FTIR) spectrometer and atomic force microscope served as control equipment.     

Conformational and dielectric analysis of hydrogen bonded polar binary mixtures of methyl benzoate with N-methylaniline

The dielectric properties of the hydrogen bonded binary system of non-associated polar liquid methyl benzoate (ester) and associated polar liquid N-methylaniline (secondary amine) were studied on both pure and equimolar binary mixtures of methyl benzoate and N-methylaniline in dilute solutions of benzene. AM 1 semi-empirical calculations were performed on various conformers of the hydrogen bonded complex. The minimum enery conformer was selected and self-consistent reaction field calculations were performed on the resultant geometry to include solvent effects. The experimental value of dipole moment is compared with the calculated value for the conformers.     

Investigation of dielectric properties and diffraction efficiency enhancements caused by photothermal effect in DR9 dye-doped nematic liquid crystal

In this work, we studied dielectric properties and laser-induced refractive index changes originating from photothermal effects of liquid crystal material doped with Disperse Red 9 (DR9) dye. Dye concentration is arranged to be between percentages changing from 0.2 wt.% to 1 wt.% in E63 nematic liquid crystal. Nonlinear optical properties such as diffraction efficiency (η) and refractive index modulation (Δn) were investigated by diffraction grating measurements. It was found the diffraction efficiency of pure E63 nematic liquid crystal is 1%. As the doping amount of DR9 dye in nematic LC is increased, diffraction efficiency took higher values and the maximum diffraction efficiency of 10% was gained with E63 doped with 0.8 wt.%DR9 dye. Moreover, dielectric permittivity and dielectric anisotropy values of the samples were investigated in the frequency range of 100 Hz-10 MHz by using dielectric spectroscopy technique. It was observed that dielectric constant values of the liquid crystal material are strongly affected by doping with dye.     

Linear and non-linear dielectric properties of a short-pitch ferroelectric liquid crystal stabilized by a polymer network

Linear and non-linear dielectric measurements were carried out on a ferroelectric liquid crystal stabilized by an anisotropic polymer network. The polymerization process was achieved at room temperature. It was performed from an achiral monomer in the ferroelectric chiral smectic C phase, exhibiting a very short helical pitch and a large polarization. The linear and non-linear dielectric spectroscopy were also completed by textural morphology as well as structural and ferroelectric characterizations. All these measurements were carried out on a pure ferroelectric liquid crystal material and on composite films containing two polymer concentrations. The increase of the polymer network density leads to a decrease of the dielectric strength determined in the linear and non-linear dielectric spectroscopy. The complementarity between the linear and non-linear dielectric measurements and their confrontation with a theoretical model allowed the simultaneous determination of some physical parameters such as macroscopic polarization, rotational viscosity and twist elastic energy. We also discuss the effect of the polymer network density on the obtained physical parameters.     

Dielectric spectroscopy of Polymer Stabilised Ferroelectric Liquid Crystals

Dielectric measurements were carried out in the frequency range from 20Hz to 500kHz on Polymer Stabilised Ferroelectric Liquid Crystals (PSFLCs). Polymerisation in the Smectic A* (Sm A*) and the Smectic C* (Sm C*) phase at equal polymer concentration results in a dielectric strength which is nearly twice the value in the latter case. An increase of the polymer concentration results in a decrease of the dielectric strength and an increase in relaxation frequency. The textural morphology and transmission intensity due to the residual birefringence of the polymer network in the isotropic phase, revealed a correlation between the interactions of the liquid crystal molecules with the polymer network. Results for polymerising in the tilted Sm C* phase with a large bias field are also reported which show that the structure of the phase in which the system was polymerised affects the dielectric properties. The observed differences in dielectric behaviour can be explained by the polymer network morphology formed due to the interplay of phase and temperature on the stabilised ferroelectric liquid crystal materials.     

Effect of surface and molecular structure on the dielectric behaviour in thick layers of cyanobiphenyl liquid crystals

The static dielectric studies of hexoxy heptoxy and octoxy cyanobiphenyl liquid crystals (6OCB, 7OCB and 8OCB) and the euteric nematic mixture of 6OCB/7OCB indicate that molecular alignment can be induced by the steel electrod surface of a dielectric thick cell with an electrode gap of about 1 mm. Whereas the permittivity values of alkyl cyanobiphenyls (6CB, 7CB and 8CB) in the nematic phase indicate imperfect alignment of the liquid crystal molecules. The good parallel molecular alignment of alkoxy cyanobiphenyls was to existence of oxygen atom in their molecular structures. These observations demonstrated a sensitive relationship between the molecular alignment, molecular structure and surface effect. Analysis of the dielectric data re-confirmed that the dipole components of the alkoxy cyanobiphenyls along the long molecular axes have a strong tendency for anti-parallel alignment which increases with increasing nematic order, whereas the dipole components perpendicular to the long molecular axes indicate a tendency for parallel alignment.     

The molecular dynamics of nematic liquid crystal confined in porous membranes treated by different surfactants

The molecular dynamics of the well-known nematic liquid crystal 4-n-pentyl-4′-cyanobiphenyl geometrically restricted in Anopore and Synpor porous membranes with various pore structure and treated by different surfactants (namely decanoic acid and lecithin) is compared. In the Anopore membrane the chosen surfactants induce the homeotropic orientation of the molecules on the walls of the cylindrical pores and observed corresponding relaxation processes (librational modes) are practically the same. The dielectric measurements of lecithin treated Synpor membranes reveals the reorientation of the molecules from planar to homeotropic on the complex multilayer structure present in their volume. The dielectric strengths of the observed two molecular processes (δ-process and librational mode) are inversed in the ratio compared to the untreated membranes. The observed differences in molecular dynamics results from the orientation of the liquid crystal molecules in untreated and treated membranes and the structure of the membranes themselves.     

Local measurement of the zenithal anchoring strength

We present an electro-optic method for measuring the zenithal anchoring strength of nematic liquid crystals, based on the determination of the distortion produced by a small electric field. This method yields the zenithal anchoring strength at small applied torques, and remarkably, only needs local measurements (optical path difference versus applied voltage, sample thickness), in contrast to the classical methods that use measurements integrated over the entire sample. We determine the zenithal anchoring strength for two nematic liquid crystals (5 CB and 5 OCB) with positive dielectric anisotropy, onto poly(tetrafluoroethylene) (PTFE) treated surfaces, that yield planar liquid crystal cells. We find that the anchoring at the PTFE-5 CB interface is strong, with an extrapolation length approximately 30 nm, and independent of temperature far enough from the isotropic transition. We observe a pretransitional weakening of the anchoring strength near the nematic-isotropic transition, due to the reduction of the orientational order parameter at the interface. With 5 OCB, we measure a stronger anchoring, with an extrapolation length approximately 15 nm. This result may be explained by the increase of the van der Waals interactions between the liquid crystal molecules and the surface, due to the presence of the oxygen atom.     

Magnetic field effects on the electric modulus properties of nematic mixture E7

The molecular dynamics of the homogeneously aligned nematic liquid crystal mixture E7 subject to a magnetic field has been studied. The dielectric spectra study has revealed a low bias magnetic field effect on the evolution of dielectric relaxation spectra occurred at lower (∼kHz) (δ-relaxation) and higher (∼MHz) (α-relaxation) frequency regions. The complex electric modulus, which converted from experimental dielectric spectra, has been analyzed with theoretical model of Debye relaxation. The obtained fitting parameters of relaxation time and strength of dielectric components are shown to vary systematically with the strength of applied magnetic field. A microscopic molecular dynamic model has been proposed to describe the two-step variation of E7 molecular under the bias magnetic field. The results provide implication for magneto-modulation of liquid crystal molecular dynamics under the bias magnetic field.     

Modeling and design of an optimized patterned electrode liquid crystal microlens array with dielectric slab

To eliminate the occurrence of disclination lines in the hole patterned electrode liquid crystal microlens array (LC MLA), inserting an ultrathin dielectric slab was proved to be an effective method. The thickness of the dielectric slab played an important role in effecting the optical performance of the liquid crystal microlens array device, including the dynamic focal range, focus diameter and symmetry of phase profile. In this paper, we studied the effect of dielectric slab thickness on the optical performance of the liquid crystal microlens array by numerical simulation. It is indicated that the optical performance of the device could be improved by reducing the dielectric slab thickness, assuming that the dielectric slab thickness was larger than the threshold thickness. The dependence of the threshold thickness on some key parameters was investigated and the associated effect on the optical performance by changing these key parameters was also studied. In the end, the approaches to enhance the optical performance, namely the dynamic focal range of the liquid crystal microlens array was proposed and proved to be in effect by numerical simulation results.     

Neural Network Based on Quantum Chemistry for Predicting Melting Point of Organic Compounds

采用反向传播神经网络与定量结构-性质关系中量子化学参数相结合的方法测定有机化合物的熔点．11个反映分子间作用力和分子对称性的描述符作为输入变量,通过分子模型和PM3半经验分子轨道理论计算量子化学参数．用260个化合物训练由MatLab方法建立的神经网络,预测了73个化合物的熔点,并与文献中的实验数据进行比较,结果表明这种人工神经网络与定量结构-性质关系结合的方法可以预测有机化合物的熔点,平均绝对偏差5%．     

溴代作用对竹红菌乙素分子性质影响的量子化学研究

用半经验量子化学方法ＡＭ１和ＰＭ３对竹红菌乙素及其溴代物进行了对比计算,考究了溴代作用对竹红菌乙素分子性质的影响,两种方法所得结果的均表明,溴代作用使分子的生成热、前线轨道能级及偶极矩等参数都有所降低,溴代作用也影响了竹红菌乙素分子内氢健的性质,并能使其对光的吸收产生红移。『     

Measurement of elastic constants of nematic liquid crystals with use of hybrid in-plane-switched cell

A new method for quick and pretty accurate measurements of splay, twist and bend elastic constants of nematic liquid crystals is experimentally verified. The main concept relies on exploiting only the electric field and determining magnitudes of nematic elastic constants from threshold fields for Freedericksz transitions in only one hybrid in-plane-switched cell. In such cell the deformations of an investigated liquid crystal are controlled by three separated pairs of electrodes confining measurement domains. In two of them inter-digital electrodes are mounted on one cell cover. Splay, twist and bend elastic constants can be measured by a proper choice of electrodes?? configuration together with orienting cover coatings (without applying magnetic fields). In this paper, we describe layout of our cells and results of experimental tests by using different liquid crystals: 5CB and 6CHBT (with positive dielectric anisotropy), Demus?? esters (with negative dielectric anisotropy) and new liquid crystals mixtures produced in our university.     

N,N-二(8-羟基-5-喹啉甲基)甘氨酸乙酯的量子化学研究

运用分子轨道理论中的半经验AM1、PM 3方法和Hartree Fock从头算方法 ,通过能量梯度全优化率先计算了新近合成的化合物N ,N 二 (8 羟基 5 喹啉甲基 )甘氨酸乙酯的平衡几何构型、电子结构以及生成热、偶极矩等分子基本性质 ,并联系经典有机电子结构理论进行讨论。三种方法得到的结构参数基本一致 ,和实验测量的晶体结构符合较好。在稳定构型基础上 ,用AM1方法进行正则振动频率分析 ,得到C—C双键、C—N单双键、C—O单双键和羟基OH的振动基频 ,和实验测得的红外光谱特征峰吻合较好     

Microwave dielectric absorption studies of hydrogen bonded polar binary mixtures of isobutanol with tertiary butyl amine

The dielectric behaviour of polar liquids like isobutanol, tertiary butyl amine and their equimolar binary mixture in nonpolar solvent benzene is studied in the microwave frequency range using the cavity perturbation technique at 6.218?GHz (J band), 9.880?GHz (X band), 16.331?GHz (P band) and 24.951?GHz (K band). Hamiltonian quantum mechanical calculations such as AM1, PM3 and MNDO optimized converged geometry operation is performed on isobutanol, tertiary butyl amine and their equimolar binary mixtures using Argus lab chemical modelling software, 2004. Dipole moments of the binary mixtures are calculated from the dielectric data using Higasi's method, and compared with the theoretical Hamiltonian quantum mechanical results. Conformational analysis of the formation of hydrogen bond between the isobutanol and tertiary butyl amine is supported by FT-IR and proton NMR spectra. The average relaxation times are calculated from their respective Cole–Cole plots.     

Sign inversion of dielectric anisotropy in nematic liquid crystal by dye doping

The present paper reports sign inversion in dielectric anisotropy of a nematic liquid crystal, i.e. 5CB, as an effect of doping dye (solvent green 3) in small amount. It is the result of strong variation of the parallel component of dielectric permittivity with temperature for a dye doped sample. This behavior is attributed to the interaction taking place between the nematic liquid crystal molecule and the dye molecule. This behavior of dielectric anisotropy has been explained on the basis of interaction between the dye (guest) and the liquid crystal molecules (host).