Kinetics of the isotropic–nematic phase transition in melted multi-component liquid crystal mixtures upon cooling

The kinetics of the phase separation and the nematic phase growth in two melted commercial multi-component liquid crystal mixtures upon cooling was studied using polarising optical microscopy and IR spectrometry. The droplets of the nematic phase revealed in the optical images across the phase transition were segmented and treated statistically. In the resulting size histograms of mixture B, two overlapping statistical ensembles related to two co-existing nematic phases were recognised; these phases were shown to be different in their chemical structures. In mixture A, any separation within the nematic phase was not found. The statistical ensembles of the nematic droplets were successfully described using the principles of irreversible thermodynamics. Analysis of the mean droplet diameter as a function of time allowed recognition of two regimes of the nematic phase evolution: (1) nucleation and rapid nucleus growth and (2) nucleus coalescence. Both the regimes were quantitatively described with the universal law for the cluster growth.     

Dielectric properties and phase transitions in crystals of TlInS x Se2 − x solid solutions

This paper reports on a study of the dielectric permittivity and electrical conductivity of single-crystal TlInS _x Se_{2 − x} solid solutions as functions of temperature and composition. It has been found that the dielectric permittivity ɛ and electrical conductivity σ decrease with increasing x and increase with growing temperature. The temperature dependences ɛ = f(T) and σ = f(T) for TlInS _x Se_{2 − x} crystals have been demonstrated to reveal anomalies in the form of maxima, which suggests that these crystals undergo phase transitions. The temperatures of the phase transitions increase with increasing x.     

Observation of cancellation and second light-induced Fréedericksz transition in nematic liquid crystals

We describe the observation of a new phenomenon: the cancellation of molecular reorientation that has been achieved in nematic liquid crystals acted on by two competing (pulsed) light beams. The effect is unstable: Starting from the cancellation condition, we have observed patterns related to the presence of a nonlinear phase shift in both beams when their intensity was increased simultaneously. We characterize the behavior of the induced phase shift as a function of the impinging power.     

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.     

Molecular rotation in liquid crystals selective deuterium spin-lattice relaxation times in the nematic mesophase of 4-cyano-4′-d17-n-octylbiphenyl

The Gibbs ensemble is used to simulate the liquid–liquid equilibria of binary mixtures containing dipolar and non-polar components.The interactions of the dipolar fluid are calculated using the Keesom intermolecular potential. The liquid–liquid coexistence properties are reported for different pressures and different combinations of dipolar/non-polar molecules. The critical properties of the mixtures are estimated. The ability of a dipole to induce phase separation is influenced by the dispersion energy of the molecule. Phase separation is enhanced if the dipolar molecule is also the component with the greatest dispersion energy.     

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.     

NMR study of the Rα structures of 2-chloro- and 2-bromothiophene partially oriented by nematic liquid crystals

The ¹H NMR spectra with the ¹³C satellites and the '3C spectra of 2-chloro- and 2-bromothiophene in nematic Merck ZLI 1167 and ZLI 1132 liquid crystal solutions were recorded and analyzed. The 'H spectra and three of the four ¹³C-satellite spectra appeared to be deceptively simple and prevented the determinations of certain individual coupling constants. As a consequence, the problems became under-determined. However, the use of two liquid crystal solvents and the assumption of unchanged structures in the solutions made it possible to determine the complete r_αr_α structures, although the linear dependence of some dipolar coupling constants led to more poorly determined groups of equations than was expected. The CH and CC distances, bond angles, and orientation matrix elements are reported for both 2-chloro- and 2-bromothiophene.     

Critical behaviour of the smectic A*–C* phase transition and electroclinic effect of ferroelectric liquid crystals with terphenyl rigid core

The SmA*–SmC* phase transition was studied by measuring the temperature and electric field dependences of the optical tilt angle, the electric polarisation and the dielectric spectra collected in a wide frequency range. Critical behaviour of the phase transition was analysed by varying the length of the fluorinated part of the alkyl terminal chain and by differing fluorine substitution in the terphenyl core. Both tilt and polarisation show tricritical mean-field behaviour for all homologues with n?>?2. Almost all coefficients that describe the SmA*–SmC* transition in the frame of the Landau theory were derived for homologue series. Double fluorine substitution in the central ring of the core seems to promote the ‘de Vries'-type smectic A*–C* phase transition with a little layer shrinkage. These well correspond with the lower tilt angle and smaller changes of the birefringence at the phase transition compared to the other homologues.     

Quasi-two-dimensional diamond crystals: Deposition from a gaseous phase and structural–morphological properties

Diamond films predominantly consisting of plane micrometer-size crystallites with a thickness of several dozen nanometers have been deposited from a methane–hydrogen gas mixture activated by a dc gas discharge. The crystallite structure has been studied by scanning and transmission electron microscopy and diffraction. A possible mechanism of formation of plane crystallites during deposition of diamond from the gas phase has been discussed. It has been shown that the results agree with the theoretical concepts of formation of crystals with a face-centered cubic lattice.     

Influence of nematic and smectic orders on polarizability of molecules of ethyl-p-(4-ethoxybenzylideneamino-)α-methyl cinnamate liquid crystals

Experimental values of the polarizability tensor γ components of molecules of ethyl-p-(4-ethoxybenzylideneamino-)α-methyl cinnamate liquid crystals in the nematic and smectic A phases have been obtained. Quadratic dependences of the longitudinal, γ _l , and transverse, γ _t , components, the mean value $\bar \gamma $ , and anisotropy Δγ in both phases have been established as functions of the orientational order parameter S of molecules in a maximally wide range of S. The nematic-smectic A phase transition with a continuous variation of S manifests itself as kinks in the linear dependences of $\bar \gamma $ , Δγ, and γ _l on S ² and does not influence the dependence γ _t (S ²). The observed dependences have been derived in the framework of the theory of the nematic-smectic A phase transition. The factors responsible for different influences of the orientational and positional orderings of molecules on the polarizability parameters have been determined.     

Anomalies in the elastic properties of silicious iron single crystals at pressures of up to 9 GPa and the α−ɛ phase transformation

A Fe+5.07 at.%Si single crystal has been studied by ultrasonic-pulse technique. Its density and elastic constants were determined for p=0 and T=293 K. The dependence of the elastic properties of silicious iron on Si concentration was constructed. The compression, the effective elastic constants, and the Grüneisen parameters were measured at hydrostatic pressures of up to 9 GPa. It was found that for p=0, and . The elastic constants c ₄₄ and c′ increase linearly with pressure by 19.3 and 18.2% by p=9 GPa. The elastic anisotropy does not vary with pressure. For p>4 GPa, c ₁₁, c ₁₂, and K _S were observed to increase nonlinearly with decreasing pressure derivative. The Grüneisen parameter γ _LA decreases with pressure down to 0.70 at 9 GPa to become negative when extrapolated to the region of the α−ɛ phase transformation. The anomalies in c ₁₁ and the negative values of γ _LA for p>11 GPa indicate that the phase transformation in silicious iron at 13.5 GPa can take place by the crystallographic mechanism of the α−ɛ transformation in pure iron, i.e. by lattice compression in the [001] direction and shearing of the (110) planes along or . An assumption is put forward that pressure gives rise in silicious iron to sp-d hybridization, which results in increased screening of the ion-ion interaction and in anomalies in elastic properties. Similar phenomena are expected to occur in pure bcc Fe as well. Fiz. Tverd. Tela (St. Petersburg) 41, 516–522 (March 1999)     

Prediction of thermodynamic and surface properties of Pb−Hg liquid alloys at different temperatures

The thermodynamic properties, such as free energy of mixing, heat of mixing, activity and structural properties, such as concentration fluctuation in long wavelength limit, short-range order parameter of Pb–Hg liquid alloy at 600 K have been calculated using theoretical modelling. It has then been correlated with modified Butler model to compute the surface tension of the alloys at different temperatures. The Pb–Hg system at 600 K is found to be ordering at higher concentration of Pb.     

Laser light scattering technique for non-invasive in situ simultaneous measurements on elastic constants and viscosity coefficients of nematic liquid crystals

Theelasticconstantsandtheviscositycoefficientsarethekeyparametersforthephysicalpropertiesofnematicliquidcrystals(LCs)[1,2],fortheyarecorrespondingtothethresholdvoltageandtherespondingtimeofliquidcrystaldisplaydevices[3,4].Sofarnotechniquethatcansimultaneouslymeasurethetwoparametersinsituhasbeenreported.TheelasticconstantsandviscositycoefficientsofnematicLCsatthepresentaremeasuredusingdifferentmethodsindependently.TheviscositycoefficientsisgenerallymeasuredwithOstwaldviscosimeter,andtheelasti…     

Effect of substituent on UV–visible absorption and photostability of liquid crystals: DFT study

The electronic transitions in the ultraviolet–visible (UV–Vis) range of two nematogens, namely 4′-cyanophenyl-4-n-pentylbenzoate and 4′-cyanophenyl-4-n-pentoxybenzoate, have been studied. The UV–Vis and circular dichroism spectra of these molecules have been simulated using the TDDFT/B3LYP/6-31+G(d) method. Mulliken atomic charges for each molecule have been compared with Loewdin atomic charges to analyze the molecular charge distribution and phase stability. The highest occupied molecular orbital and lowest unoccupied molecular orbital energies corresponding to the electronic transitions in the UV–Vis range have been reported. The excited states have been calculated via configuration interaction singles with semi-empirical Hamiltonian ZINDO (Zerner's intermediate neglect of differential overlap method). Further, the effect of substituent on ultraviolet absorption and photostability of the molecules has been discussed. The photostability of the molecules has been investigated in order to understand the application and operation with ultraviolet and visible light regions.     

Absorption and emission properties of phenylene ethynylene oligomers: effect of substitution and π-conjugation length

The optical properties of a series of π-conjugated phenylene-ethynylene oligomers (OPEs) have been studied by advanced quantum chemical methods. The ground state and lowest singlet excited state geometries of unsubstituted and different electron donor and acceptor groups substituted OPEs are optimized by density functional theory and configuration interaction singles methods. The absorption and emission spectra of unsubstituted and substituted OPEs have been calculated using the time-dependent density functional theory (TDDFT) method. The results of theoretical calculations are in good agreement with the available experimental results. It has been found that the substitution of electron donating and withdrawing groups in the phenyl ring and conjugation length of the OPEs has significantly affect both the absorption and emission spectra     

Optical spectra of triglycine sulfate crystals in the range of 7–33 eV and its changes at phase transition

Pseudo-dielectric functions ?ε₁(E)? and ?ε₂(E)? of triglycine sulfate (TGS) crystal have been obtained in the range of 7–33 eV for different temperatures close to ferroelectric phase transition by spectral ellipsometry using the synchrotron radiation source BESSY II. These dielectric functions ε₁(E) and ε₂(E) have also been calculated from first principles using CASTEP CAmbridge Serial Total Energy Package code together with the band structure and density of electronic states of the crystal. Experimental and theoretical dielectric functions agree satisfactorily. A characteristic decrease of temperature dependences of the dielectric losses tgδ(T) and related values just below the phase transition temperature T _c have been found and discussed.     

Geometric phases and quantum phase transitions in inhomogeneous XY spin-chains:Effect of the Dzyaloshinski-Moriya interaction

We study geometric phases of the ground states of inhomogeneous XY spin chains in transverse fields with Dzyaloshinski--Moriya (DM) interaction, and investigate the effect of the DM interaction on the quantum phase transition (QPT) of such spin chains. The results show that the DM interaction could influence the distribution of the regions of QPTs but could not produce new critical points for the spin-chain. This study extends the relation between geometric phases and QPTs.