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1.
The 2H-N.M.R. spectra of mixtures of the non-mesogenic compound 4-cyano-4′-methylbiphenyl (1CB) and the nematic liquid crystal 4-cyano-4′-n-pentylbiphenyl (5CB) are measured as a function of concentration and temperature. Concentrations of up to 25 mol% 1CB have no effect on the N.M.R. spectrum and therefore on the orientational order of 5CB at a given reduced temperature. The order matrix of the 1CB is calculated from the measured quadrupole couplings. The results are analysed in terms of a model for orientational order that includes two anisotropic terms: (a) interaction between the molecular quadrupole moment and the mean electric field gradient of the medium, and (b) short range repulsive interactions. An estimate of the molecular quadrupole moment tensor of 1CB is obtained from the analysis. 相似文献
2.
G. L. Hoatson A. L. Bailey A. J. van der Est G. S. Bates E. E. Burnell 《Liquid crystals》1988,3(6):683-694
Deuteron magnetic resonance spectroscopy (2H-N.M.R.) has been used to investigate the effect of the nematic environment on the flexibility and orientational order of two perdeuteriated cyanobiphenyl homologues: 4-methyl-4'-cyanobiphenyl (1CB-d11) and 4-n-pentyl-4'-cyanobiphenyl (5CB-d19). The systems studied were low concentrations of 1CB-d11 and 5CB-d19 dissolved in the nematic phases of 5CB, N-(-4-ethoxybenzylidene)-4'-n-butylaniline (EBBA), Merck ZLI-1132 (1132) and a 55wt% mixture of 1132: EBBA. The spectra are dramatically different in these environments. Previous studies on small solutes have suggested that in the 55wt% 1132: EBBA mixture (at 301.4 K) the dominant orienting mechanism depends on the size and shape of the molecule which suggests that it is a short range repulsive interaction. This interaction has been modelled by treating the liquid crystal as an elastic continuum and the solute as a collection of van der Waals spheres which stretch the liquid crystal in the two dimensions perpendicular to the director. The distortion of the liquid crystal depends on the dimensions of the solute, and the elastic energy is described in terms of a Hooke's law force constant, k. The model is extended to include flexible liquid crystal molecules and quadrupolar couplings are calculated for each conformation of the 5CB chain. Statistical averaging over all conformations gives an excellent fit to the experimental spectrum. The results for 1CB and 5CB show that in the other nematic phases contributions from additional mechanisms must be included. Previous studies of 2H2 and other solutes indicate that the additional mechanism is the interaction between the solute molecular quadrupole moment and the mean electric field gradient of the liquid crystal. 相似文献
3.
Previous studies using dideuterium as a solute have demonstrated the importance for orientation of the interaction between the solute molecular quadrupole moment and the average electric field gradient present in liquid crystals. With the aim of learning about additional orientational mechanisms, we have studied the temperature dependence of the 2H-NMR spectra of the liquid crystal 5CB-d19 as the solute in three liquid crystal mixtures: 55 wt % 1132/EBBA, 56·5 wt % 1132/EBBA and 70 wt % 5CB/EBBA. In these mixtures, the contribution from the environment to the average electric field gradient at the 2H nucleus of dideuterium is zero. The spectra of 5CB-d19 in the mixtures 55 wt % 1132/EBBA and 56·5 wt % 1132/EBBA are equivalent, but are different from those in 70 wt % 5CB/EBBA. The spectra of 5CB in 55 wt % 1132/EBBA and 70 wt % 5CB/EBBA are analysed using two different models for the short range potential, and param eters of the models are used to compare the potentials in the different mixtures. For a given spectral splitting of the chain C1 deuteron, the reduced short range potential is the same in all three mixtures studied. The spectral differences observed are a consequence of different nematic-isotropic phase transition temperatures combined with the effect of trans/gauche-isomerization in the hydrocarbon chain. 相似文献
4.
The orientational ordering of the liquid crystal, 3M2CPHOB ((2S, 3S)-3-methyl-2-chloropentanoic acid-4',4'-hexyloxybiphenyl ester) in its smectic A and chiral smectic C phases has been studied by carbon-13 2D N.M.R. The technique used is separated local-field spectroscopy, which produces a first-order splitting for each carbon signal, from which carbon-proton dipolar constants can be determined. The order parameters for different molecular segments of the liquid crystal can then be calculated. The C-H bond order parameter at the chiral centre with a chlorine atom is unusually large, which is a strong indication of hindered rotation of the molecular segment at the chiral centre. The carbon-13 chemical shifts of 3M2CPHOB were also measured as a function of temperature, and the relation between the chemical shifts and the order parameters is discussed. 相似文献
5.
We present a molecular dynamics simulation study in which we determined the melting point of ice I(h) for the polarizable SWM4-NDP water model (Lamoureux et al., Chem. Phys. Lett., 2006, 418, 245-249) and compared the performance of several popular water force fields, both polarizable and nonpolarizable, in terms of melting temperature, stability and orientational structuring of ice. The simulations yield the melting temperature of SWM4-NDP ice as low as T(m) = 185 ± 10 K, despite the quadrupole moment of a SWM4-NDP water molecule being close to the experimental gas phase value. The results thus show that the dependence of T(m) on the molecular quadrupole, observed for the three- and four-site water models, is generally lost if polarization is explicitly included. The study also shows that adding polarizability to a planar three-charge water model increases orientational disorder in hexagonal ice. In addition, analysis of the tetrahedral order in bulk ice reveals a correlation between the pre-existing degree of orientational disorder in ice simulated using different polarizable and nonpolarizable models and the melting temperature of the models. Our findings thus suggest some new considerations regarding the role of polarization forces in a crystalline solid that may guide future development of reliable polarizable water models for ice. 相似文献
6.
Vecchi I Arcioni A Bacchiocchi C Tiberio G Zanirato P Zannoni C 《The journal of physical chemistry. B》2007,111(13):3355-3362
We have explored the changes in the phase stability, orientational order, and dynamics of the nematic 4-cyano-4'-n-pentylbiphenyl (5CB) doped with either the trans or the cis form of different p-azobenzene derivatives using the ESR spin-probe technique. In particular, we have studied the effects induced by each of the seven nonmesogenic 4-R-phenylazobenzenes (R = H, F, Br, CH3, CF3, On-Bu, Ot-Bu) at 1% and 7% mole fraction on the order parameter and on the shift of the nematic-isotropic transition temperature (TNI), as reported by a nitroxide spin probe, and we have tried to relate them to the solute shape and charge distribution. In all the cases the presence of the azo-derivative causes a depression of T(NI), more pronounced for the cis isomers. The dependence of on the reduced temperature T* = T/T(NI) remains the same as that of pure 5CB in all trans-doped samples at 1% and 7% and decreases only slightly in the cis at 1%. However, we observe different and in some cases large variations (up to 25%) in for the cis at 7%, showing solute effects that go beyond the shift in T(NI). Surprisingly enough, even at the highest concentration, the probe dynamics appears to be essentially independent of the nature, the configuration, and the concentration of the different solutes and very similar to that observed in the pure 5CB. 相似文献
7.
G. L. Hoatson A. L. Bailey A. J. van der Est G. S. Bates E. E. Burnell 《Liquid crystals》2013,40(6-7):683-694
Abstract Deuteron magnetic resonance spectroscopy (2H-N.M.R.) has been used to investigate the effect of the nematic environment on the flexibility and orientational order of two perdeuteriated cyanobiphenyl homologues: 4-methyl-4′-cyanobiphenyl (1CB-d 11) and 4-n-pentyl-4′-cyanobiphenyl (5CB-d 19). The systems studied were low concentrations of 1CB-d 11 and 5CB-d 19 dissolved in the nematic phases of 5CB, N-(-4-ethoxybenzylidene)-4′-n-butylaniline (EBBA), Merck ZLI-1132 (1132) and a 55wt% mixture of 1132: EBBA. The spectra are dramatically different in these environments. Previous studies on small solutes have suggested that in the 55wt% 1132: EBBA mixture (at 301.4 K) the dominant orienting mechanism depends on the size and shape of the molecule which suggests that it is a short range repulsive interaction. This interaction has been modelled by treating the liquid crystal as an elastic continuum and the solute as a collection of van der Waals spheres which stretch the liquid crystal in the two dimensions perpendicular to the director. The distortion of the liquid crystal depends on the dimensions of the solute, and the elastic energy is described in terms of a Hooke's law force constant, k. The model is extended to include flexible liquid crystal molecules and quadrupolar couplings are calculated for each conformation of the 5CB chain. Statistical averaging over all conformations gives an excellent fit to the experimental spectrum. The results for 1CB and 5CB show that in the other nematic phases contributions from additional mechanisms must be included. Previous studies of 2H2 and other solutes indicate that the additional mechanism is the interaction between the solute molecular quadrupole moment and the mean electric field gradient of the liquid crystal. 相似文献
8.
P. L. Praveen N. Ajeetha D. P. Ojha 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2010,84(2):229-234
A comparative computational analysis of molecular ordering in homologous series of monotropic nematic liquid crystal 4′-n-alkyl-4-cyanobiphenyl (nCB) molecules with alkyl groups, butyl (4CB), pentyl (5CB), hexyl (6CB), heptyl (7CB), has been carried out with respect to
translational and orientational motion. The atomic net charge and dipole moment at each atomic center were evaluated using
the complete neglect differential overlap (CNDO/2) method. The modified Rayleigh-Schrodinger perturbation theory and the multicenter-multipole
expansion method were employed to evaluate long-range intermolecular interactions, while a 6-exp potential function was assumed
for short-range interactions. Various possible geometrical arrangements of molecular pairs with regard to different energy
components were considered, and the most favorable configuration was found. A comparative picture of molecular parameters,
such as total energy, binding energy, and total dipole moment of 4CB, 5CB, 6CB, and 7CB, is given. The results are discussed
in the light of other theoretical observations. 相似文献
9.
The influence of force field details in all-atom molecular dynamics (MD) simulations on the predicted thermodynamic, structural, and dynamic properties of bulk 4-cyano-4?-pentylbiphenyl (5CB) systems have been investigated in the 292–368 K temperature range. The effect of the molecular dipole moment and the details of dihedral potential for biphenyl unit were investigated using both polarisable (POL) and non-polarisable (NP) versions of the quantum chemistry-based force field. The predicted densities for the nematic and isotropic phases of bulk 5CB were found to be in excellent agreement with available experimental data. The nematic-isotropic transition temperature (TNI) showed strong sensitivity to the force field details, MD simulations with partial atomic charge distributions and molecular dipole moment corresponding to high-level quantum chemistry calculations predicted an overestimation of the TNI by about 30 K. Rescaling the charges to allow the molecular dipole to be closer to experimentally reported values of 5CB dipole in condensed phases, significantly improved the prediction of TNI as well as other thermodynamic and dynamic properties of 5CB. We also discuss how the structural, thermodynamic, and dynamic properties of bulk 5CB are affected by the flexibility of the central biphenyl dihedral and the inclusion of induced polarisation effects. 相似文献
10.
Experimental studies of phase diagram and morphology of mixtures composed of linear poly(2-ethylhexylacrylate) (poly-2EHA) of molecular weight Mw = 92000g/mol and E7, an eutectic blend of nematic liquid crystals (LCs), were performed. The latter consists of four cyanoparaphenylenes, i.e. 4-cyano-4?-n-pentyl-biphenyl (5CB), 4-cyano-4?-n-heptyl-biphenyl (7CB), 4-cyano-4?-n-oxyoctyl-biphenyl (8OCB) and 4-cyano-4?’-n-pentyl-p-biphenyl (5CT). Thermal properties of the poly-2EHA/E7 system were studied by differential scanning calorimetry and the sample morphologies were investigated by optical microscopy. Phase diagram analysis revealed an increase of the nematic–isotropic transition temperature when E7 was added to poly-2EHA, compared to pure E7. This effect, related to a preferential miscibility phenomenon of E7 components towards poly-2EHA, was evidenced by gas chromatography analysis coupled to mass spectrometry, allowing to qualify and quantify the content of phase separated LC domains. Thermograms of model LC mixtures including 5CB, 7CB, 8OCB and 5CT, which correspond to their composition in segregated LC domains of poly-2EHA/E7, present strong deviations from eutectic behaviour. In order to access the impact of such variations for practical applications, such a model LC mixture was introduced in photochemically crosslinked 2-EHA (polycross-2EHA). Surprisingly, the electro-optical response of the obtained polycross-2EHA/LC films was considerably improved compared to the original polycross-2EHA/E7 system. 相似文献
11.
Donata Catalano Claudia Forte Carlo Alberto Veracini J. W. Emsley G. N. Shilstone 《Liquid crystals》1987,2(3):357-371
The orientational order parameters have been measured by deuteron N.M.R. of both solute (at low dilution) and solvent in various binary mixtures involving the liquid crystal 4,4'-di-n-heptylazoxybenzene (HAB). The solutes studied were azoxybenzene-d10 and n-heptylbenzene-d7 which are fragments of HAB, azobenzene-d10 because of its similarity to azoxybenzene, and anthracene-d10 because of its known structure and symmetric shape. The major and biaxial order parameters of the solutes are analysed in terms of a molecular field model for the potential of mean torque for biaxial particles. The behaviour of the solute order parameters on approaching and entering the smectic A phase is interpreted in terms of a temperature and phase dependent partitioning of the solute between aromatic and aliphatic regions of the solvent. 相似文献
12.
Using the in situ measurements of the surface potential built across the evaporated liquid crystalline 4-n-pentyl-4'-cyanobiphenyl (5CB) films on metal electrodes with different work functions, we studied the cooperative molecular field effect (CMFE) that assists carrier injection from electrodes and the induced orientational reordering in evaporated liquid crystalline molecules on metals. The surface potential increased, and then became constant after the 5CB monomolecular layer was formed. It was shown that the CMFE accompanying orientational reordering accounts for the metal work function dependence of the surface potential. Finally, the orientational reordering is discussed in terms of the anchoring energy. 相似文献
13.
We have studied the orientational order of the monomer 4-n-pentyl-4'-cyanobiphenyl (5CB) and of the dimer, [PtCl2(5CB)2], formed by linking two cyanobiphenyl units via a platinum dichloride bridge, dissolved in a common nematic solvent, using deuterium NMR spectroscopy. Analysis of the second rank order parameters, obtained from these experiments, in terms of a molecular field theory yields the anisotropic solute-solvent strength parameter responsible for the solute alignment. In the limit of low solvent order the strength parameters for the monomer and dimer differ significantly, in accord with the differing anisotropies of these two solutes. However, as the solvent order increases, so the relative difference in the strength parameters decreases, tending to zero. A possible explanation for this intriguing behaviour is proposed. 相似文献
14.
Lars Holländer Wilhelm Kossack Matthias Kollosche Werner Wirges Friedrich Kremer Reimund Gerhard 《Liquid crystals》2016,43(10):1514-1521
Polymer-dispersed liquid crystals (PDLCs) of ferroelectric poly(vinylidene fluoride-trifluoroethylene) and nematic 4-cyano-4?-n-hexylbiphenyl (6CB) or 4-cyano-4?-n-pentylbiphenyl (5CB) were prepared to study the effect of the remanent polarisation of the polymer on the liquid crystal alignment. We measured the macroscopic alignment of the liquid crystal molecules in the thickness direction by means of Infrared Transition-Moment Orientational Analysis. Electrical poling at 100 V/µm caused an increased order parameter up to 0.15. After subsequent annealing above the nematic-to-isotropic phase-transition temperature, the order parameter was reduced to 0.02. Nevertheless, the order parameter was still higher than for non-poled film indicating a slight orientation in thickness direction. Both values are lower than those expected from model calculations. In agreement with dielectric measurements, we attribute this result to the shielding effect of mobile charge carriers within the liquid crystal inclusions. 相似文献
15.
A simple statistical model of interacting non-rigid molecules, based on a perturbation expansion of the pair correlation function and the additivity of segmental interactions, is applied to the study of orientational order as measured by N.M.R. in the nematic and SA phases of 4-n-alkyl-4'-cyanobiphenyls (N-CB, N = 5 to 8), the nematic and SC phases of 4-n-alkyloxybenzoic acids (N-OBA, N = 7, 8) and the Dh0 columnar discotic phase of hexa-alkyloxytriphenylenes (N-THE, N = 5 to 8). The order parameters of each homologous series are correctly described in terms of two isotropic and two anisotropic segmental coupling constants. The model predicts certain relations among coupling constants pertaining to different homogous series. These predictions are supported by the results obtained for the three types of compounds studied. 相似文献
16.
The molecular orientational order of a side chain thermotropic nematic polymer has been measured by proton NMR. The alignment of the side chains is reflected in the splitting of the NMR signal into a doublet. Simultaneous orientational effects of magnetic and electric fields on the mesogenic groups were studied in magnetically preoriented layers. Temperature, twist angle and thickness dependences of the spectra were measured. The order parameter S and the parameter of orientational order S' of the samples were estimated. 相似文献
17.
Jeong-Mim Han Jeoung-Yeon Hwang Dae-Shik Seo Sang-Keuk Lee Joon-Ung Lee 《Liquid crystals》2004,31(9):1259-1264
The washing effects on liquid crystal (LC) alignment capability in a NLC, 4-n-pentyl-4'-cyanobiphenyl (5CB), on a rubbed polyimide (PI) surface containing the trifluoromethyl moiety were studied. The extrapolation length de of 5CB on the rubbed PI surface decreases with the rubbing strength RS. Also, the large extrapolation length de of 5CB for washing with IPA was measured at RS=114 mm. The polar anchoring energy of 5CB on the rubbed PI surface was decreased by the washing process; it increased with the rubbing strength RS on the PI surface. The surface order parameter SS of 5CB for all the washing processes is smaller than for the non-washing process. Consequently, the polar anchoring energy and surface order parameter Ss in 5CB are largely attributed to washing effects. 相似文献
18.
In this study, a new method for the detection of heavy metals in aqueous phase was developed using liquid crystals (LCs). When UV-treated nematic LC, 4-cyano-4'-pentyl biphenyl (5CB) that was confined in the urease-modified gold grid was immersed in a urea solution, an optical response from bright to dark was observed under a polarized microscope, indicating that a planar-to-homeotropic orientational transition of the LC occurred at the aqueous/LC interface. Since urease hydrolyzes urea to produce ammonia, which would be ionized into ammonium and hydroxide ions, the main product of the photochemically degraded 5CB, 4-cyano-4'-biphenylcarboxylic acid (CBA), was deprotonated and self-assembled at the interface, inducing the orientational transition in the LC. Due to the high sensitivity and rapid response of this system, detection of heavy metal ions was further exploited. The divalent copper ion, which could effectively inhibit the activity of urease, was used as a model heavy metal ion. The optical appearance of the LC did not change when urea was in contact with the copper nitrate hydrate-blocked urease. After the copper-inhibited urease was reactivated by EDTA, a bright-to-dark shift in the optical signal was regenerated, indicating an orientational transition of the LC. This type of LC-based sensor shows high spatial resolution due to its optical characteristics and therefore could potentially be used to accurately monitor the presence of enzyme inhibitors such as heavy metal ions in real-time. 相似文献
19.
本文提出液晶/水界面上氢键作用可以诱导热致型液晶(戊基联苯氰,简称: 5CB)发生取向转变.当液晶5CB膜接触酚类(如对硝基苯酚)水溶液的时候,由于酚类物质的酚羟基与液晶5CB分子中的氰基在液晶水界面上形成了氢键,在氢键的作用下使得液晶5CB由平行取向转变成了垂直取向.此外,还利用了液晶传感器可视化了酚类物质与牛血清蛋白(BSA)之间的相互作用.本文的研究结果可为研究液晶/水界面上的界面现象提供新的思路,并且有望开发出基于氢键作用的液晶生物化学传感技术. 相似文献
20.
We have carried out very accurate density measurements (with a precision of ±5 × 10-5g cm-3) near the smectic A-nematic transition in binary mixtures of 4-n-nonyl-4'-cyanobiphenyl (9CB) and 4-n-decyl-4'-cyanobiphenyl (10CB). The transition crosses over from second to first order as the temperature range of the nematic phase decreases. For mixtures with the shortest nematic range the data deviate noticeably from a single power law behaviour. Such a deviation is an indication of the first order nature of the transition. Very good fits to a single power law have been obtained for pure 9CB and the x = 0·04 mixture where x is the mole fraction of 10CB in 9CB. The critical exponent obtained from the power law fitting has enabled us to locate the tricritical point to be very close to x=0·04, which is in agreement with the results obtained previously by high resolution calorimetric [1] and X-ray scattering studies [2]. 相似文献