Reexamining the phase diagram of the Gay—Berne fluid

This work reexamines and updates earlier investigations on the phase behaviour of the Gay-Berne liquid crystal model, concentrating on the effect of varying temperature. Constant volume and constant pressure Monte Carlo simulations are combined for systems consisting of N = 500 molecules along different isotherms over the reduced temperature range 0.60 ≤ T ≤ 1.25. As in previous simulation studies of the model, the study identifies nematic and smectic B phases on compressing the isotropic fluid, the particular phase sequence depending on temperature. The nematic phase is found to be stable with respect to the isotropic phase for reduced temperatures T ≥ 0.75. In the temperature range 0.75 ≤ T ≤ 1.25, the phase boundaries of the isotropic-nematic transition are obtained by computing the Helmholtz free energy of both phases from thermodynamic integration. From the simulation data, the relative volume change at the isotropic-nematic transition is about 2%, and this value appears to be rather insensitive to changes in temperature. On compressing the nematic phase, the Gay-Berne fluid undergoes a strong first-order transition to the smectic B phase. This transition is studied by using constant pressure simulation, and the coexistence properties are estimated from the limits of mechanical stability of the nematic phase. Larger relative volume changes are found at the transition than those suggested by previous studies, with typical values increasing up to 10.5% as the temperature is decreased. The results are consistent with the existence of strong coupling between nematic and smectic order parameters. For temperatures T ≤ 0.70 the nematic phase is no longer stable, and the phase sequence isotropic-smectic B is observed. Therefore, the Gay-Berne model exhibits an isotropic-nematic-smectic B triple point. Extrapolating the present simulation data, this triple point is located approximately at reduced temperature T_INB ? 0.70 and reduced pressure P_INB ? 1.825.     

Effect of density variation on the Sm A–I phase transition properties

Based on a thermodynamic model, we investigate how the density variation influences the smectic (Sm A)–isotropic (I) phase transition. We find that the density variation shifts the smectic A–isotropic transition temperature, however, first-order nature of the transition remains the same. Here, we also examine the effect of high pressure on the thermodynamic quantities. The present analysis shows that the pressure strongly influences the enthalpy and density step at the clearing transition. The pressure dependence of the thermodynamic properties is incorporated through the pressure dependent second Landau coefficient and the coefficients which couple the nematic and smectic order parameters to the density. We find a close agreement between theoretical and experimental results. Furthermore, we discuss the implications of the results for achiral liquid crystals.     

First order phase change during isotropic-nematic and nematic-smectic a transitions of NPOB

The temperature variation of the magnetic susceptibility (χ) of NPOB are reported in isotropic, nematic and smectic A phases, χ and Δχ undergo sudden changes at the phase transitions. The isotropic-nematic and nematic-smectic A transitions are assigned to be first order phase transition.     

Electro-optical Kerr effect in the isotropic phase of the two antiferroelectric liquid crystal mixtures

We have experimentally studied for the first time the electro-optical Kerr effect and the pre-transitional behavior in the isotropic phase of two antiferroelectric liquid crystal mixtures, W-232 and W-204D, composed of rod-like ester molecules exhibiting the direct smectic-A to isotropic (SmA-I) phase transition. The Kerr law has been confirmed for the two compounds and the variation of inverse Kerr constant with temperature above the smectic–isotropic transition temperatures were determined. Both the mixtures with very broad antiferroelectric phase around room temperature have similar sequence of the phases (i.e., Cr-SmC*A-SmC*-SmA-I). Although, the pre-transitional behavior is usually complex in the isotropic phase of the chiral smectic liquid crystal compounds, the investigated compounds showed a similar behavior compared to that of nematic–isotropic behavior.     

Dirty, skewed, and backwards: the smectic A-C phase transition in aerogel

We study the smectic A-C transition in anisotropic and uniaxial disordered environments, e.g., uniaxially stretched aerogel. We find very strange behavior of translational correlations: the low-temperature, lower-symmetry smectic C phase is less translationally ordered than the high-temperature, higher-symmetry smectic A phase, with short ranged and algebraic translational correlations, respectively. Specifically, the A and C phases belong to the quasi-long-ranged translationally ordered "XY Bragg glass" and short ranged translationally ordered "m=1 Bragg glass" phase, respectively. The A-C phase transition itself belongs to a new universality class, whose fixed points and exponents we find in a d=5-epsilon expansion.     

Comparative study of liquid-crystalline ordering in a monomer,linear polymer,and graft copolymer by the photon transmission technique

The photon transmission technique was used to study the phase transitions of a liquid crystalline acrylate monomer, 6-(4-cyanobiphenyl-4′oxy)hexyl acrylate (LC6), its homopolymer (PLC6) and its graft copolymer (GLC6) with polytetrahydrofuran grafts. The phase transitions were also confirmed by DSC and polarizing microscopy. We observed the phase transition sequence isotropic–nematic–smectic A–smectic C in the LC6 monomer. In PLC6 and GLC6 polymers, the nematic and smectic A phases appear dominant. The apparent nematic–smectic A transition is of first order in PLC6 and of second order in GLC6, with the transition temperature remaining the same. The effects of quenched random constraints introduced in GLC6 are consistent with the theory of quenched random interactions. The critical exponents were also evaluated.     

Design,synthesis and characterization of a linear hydrogen bonded homologous series exhibiting reentrant smectic C ordering

Design, synthesis and characterization of seven linear hydrogen bonded liquid crystal complexes derived from mesogenic p–n-decyloxy benzoic acid and p–n-alkyl benzoic acids designated as 10OØn (where n varied from ethyl to octyl) are reported. FTIR studies confirm the hydrogen bond formation in all these complexes. The phase transition temperatures and their corresponding enthalpy values are experimentally deduced from Differential Scanning Calorimetry (DSC) studies. POM and DSC data are further utilized for the construction of 10OØn phase diagram. Two Odd–even effects have been evinced, one in enthalpy values and the other in corresponding transition temperatures across the isotropic to nematic phase transition. An interesting result is the observation of re-entrant smectic ordering, designated as smectic C_R in three higher ordered mesogens. A new smectic ordering, smectic X, has been observed which is sandwiched between traditional smectic C and re-entrant smectic C_R. Magnitudes of optical tilt angle in smectic C, smectic X and smectic C_R are experimentally found to attain saturation with decrement of temperature in the corresponding phase. The occurrence of smectic X and smectic C_R are discussed with relation to the molecular chemical structure. The optical filtering action in smectic C and re-entrant smectic C_R phases have been analyzed.     

Dielectric studies in N- (p-n-butoxybenzylidene) p-n-butylaniline

The dielectricconstant variation with temperature of N-(p-n-butoxybenzylidene)p-n-butylaniline is presented in the isotropic, nematic, smectic A and smectic B phases. A new transition in the nematic phase is reported. The derived parameter, molar susceptibility anisotropy, Δσ, is also determined.     

Density studies across the smectic G-nematic and nematic-lsotropic transitions

The densities of N(p-n-pentyloxy benzylidene) p-ethylaniline and N(p-n-hexyloxy benzylidene) p-ethylaniline are measured as a function of temperature from the isotropic liquid to the smectic G phase. Both the compounds exhibit enantiotropic smectic G and nematic liquid crystalline phases. The changes in density across the phase transformations and the thermal expansion coefficient confirm the order of the transitions as of first order. The particular importance of the smectic G to nematic transformation is apparent from the density jump across the transition. An estimate of the pressure dependence of the isotropic-nematic transition temperature is found to be in reasonable accord with the literature data.     

129Xe diffusion in a ferroelectric liquid crystal

Measurements of ¹²⁹Xe self-diffusion and shielding as a function of temperature were performed to cover the different phases of the ferroelectric liquid crystal FELIX-R&;D. The shielding data prove untwisting of the helical structure in the nematic phase (i.e. non-chiral nematic phase) of FELIX-R&;D. Self-diffusion measurements were carried out in a direction parallel to the main magnetic field of the NMR spectrometer. However, in order to yield the anisotropy of the xenon self-diffusion tensor a few measurements also were performed in the perpendicular direction. A special technique, based on the observation of the second spin echo instead of the conventional first one, was applied to avoid convection problems. The experiments reveal all the phase transitions and a continuous decrease in the self-diffusion constant along the external magnetic field, D‖, when moving from the isotropic to the smectic C? phase. The respective activation energy E‖ appears to vary remarkably, however, being about the same in the isotropic and smectic C? phases. In the smectic mesophases significantly faster xenon self-diffusion was detected in the perpendicular direction than in the parallel direction. The detected self-diffusion constant D ⊥ in the perpendicular direction seems to remain almost constant in the smectic mesophases and close to the value of the self-diffusion constant in the isotropic phase. The results are in agreement with the structural features of smectic phases and indicate redistribution of xenon atoms towards the interlayer space of smectic mesophases.     

Positron lifetimes in five phases of BEA

Positron lifetimes have been measured as a function of temperature in 4-butyloxybenzal-4′-ethylaniline (BEA). BEA has been previously reported to have two liquidcrystalline phases (smectic and nematic) with transition temperatures as follows: solid → smectic, 40.5° C; smectic → nematic, 51.0° C; and nematic → isotropic liquid, 65.5° C. Positron life time spectra were resolved into two components, with the shorter component τ₁ remaining approximately constant in all phases, and τ₂ exhibiting reversible changes at all of the above transitions. In addition, an irreversible discontinuity in the τ₂ lifetime was observed in the vicinity of 28° C, indicating the presence of a new phase (phase X) of BEA. The τ₂ andI ₂ values obtained for the various phases of BEA are: solid (1.25 nsec, 7.1%), phase X (1.97 nsec, 26.2%), smectic (2.36 nsec, 23.6%), nematic (2.72 nsec, 28.3%), and isotropic liquid (2.69 nsec, 29.8%).     

Stress anisotropy in liquid crystalline phases

Monte Carlo simulations of bulk liquid crystals in the isotropic, nematic and smectic phases were performed. The simulations were carried out using different box shapes. The diagonal components of the pressure tensor were calculated to verify that the system is in mechanical equilibrium. For simulations in cubic boxes it was found that the three components of the pressure tensor had the same values in the isotropic and nematic phases but they were different in the smectic phase, i.e. the system seemed to be under anisotropic stress. NVT and NPT simulations in the smectic phase were performed by allowing the box sides to fluctuate independently; in this case, the average diagonal components of the pressure tensor had the same value. Inaccurate calculation of the total pressure produces incorrect equilibrium boundaries in the phase diagram. Microphases and poorly defined layering can be found in simulations of smectic phases when they are performed on cubic boxes. Although the pressure anisotropy is relaxed out, the layering structure in smectic phases seems to depend on the initial configuration, regardless of the simulation method.     

Phase diagram involving the mesomorphic behavior of binary mixture of sodium oleate and orthophosphoric acid

The present investigation deals with the binary mixture of two non-mesogenic compounds, viz. sodium oleate (Naol) and orthophosphoric acid (H₃PO₄) which exhibits very interesting liquid crystalline smectic phases at large range of concentrations and temperature. The mixtures with concentrations ranging from 10% to 90% Naol in H₃PO₄ exhibit SmA, SmC, SmE and SmB phases, sequentially when the specimen is cooled from its isotropic phase. Physical properties, such as ultrasonic velocity, adiabatic compressibility and molar compressibility, show anomalous behavior at the isotropic to mesosphase transition.     

Surface freezing and a two-step pathway of the isotropic-smectic phase transition in colloidal rods

We study the kinetics of the isotropic-smectic phase transition in a colloidal rod/polymer mixture by visualizing individual smectic layers. First, we show that the bulk isotropic-smectic phase transition is preceded by a surface freezing transition in which a quasi-two-dimensional smectic phase wets the isotropic-nematic interface. Next, we identify a two-step kinetic pathway for the formation of a bulk smectic phase. In the first step a metastable isotropic-nematic interface is formed. This interface is wetted by the surface-induced smectic phase. In the subsequent step, smectic layers nucleate at this surface phase and grow into the isotropic bulk phase.     

Effect of shape anisotropy on the phase diagram of the Gay-Berne fluid

We have used the density functional theory to study the effect of molecular elongation on the isotropic-nematic, isotropic-smectic A and nematic-smectic A phase transitions of a fluid of molecules interacting via the Gay-Berne intermolecular potential. We have considered a range of length-to-width parameter 3.0 ⩽ x₀ ⩽ 4.0 in steps of 0.2 at different densities and temperatures. Pair correlation functions needed as input information in density functional theory are calculated using the Percus-Yevick integral equation theory. Within the small range of elongation, the phase diagram shows significant changes. The fluid at low temperature is found to freeze directly from isotropic to smectic A phase for all the values of x₀ considered by us on increasing the density while the nematic phase stabilizes in between isotropic and smectic A phases only at high temperatures and densities. Both isotropic-nematic and nematic-smectic A transition density and pressure are found to decrease as we increase x₀. The phase diagram obtained is compared with computer simulation result of the same model potential and is found to be in good qualitative agreement.     

Sequence of four orthogonal smectic phases in an achiral bent-core liquid crystal: evidence for the SmAP(α) phase

The mesomorphic properties of an achiral bent-core liquid crystal derived from 4-cyanoresorcinol are studied by polarizing optical microscopy, x-ray diffraction, and second harmonic electro-optic response. It shows a novel sequence of four nontilted or orthogonal smectic phases on cooling: SmA-SmAP(R)-SmAP(X)-SmAP(A). Here SmAP(X) is the new orthogonal polar uniaxial smectic phase. The electric-field-induced transformations in the SmAP(X) phase give rise to two biaxial states separated by a uniaxial one. The second harmonic electro-optic response in this phase is interpreted in terms of the polar interaction with the electric field. A comparison of the experimental results with the next-nearest-neighbor model for the structure of the SmAP(X) phase shows it to be an SmAP(α) phase.     

Chain dynamics in a chiral C phase by deuteron spin relaxation study

Molecular reorientations and internal conformational transitions of an aligned chiral liquid crystal (LC) 10B1M7 are studied by means of deuterium spin-lattice relaxation in its smectic A (SmA) and smectic C* (SmC*) phase. The motional model which is applicable to uniaxial phases of many LCs is found to be adequate even when the phase is a tilted SmC* phase. The deuterium NMR spectrum in this phase cannot discern rotations of the molecular director about the pitch axis. The basic assumption is that the phase biaxiality is practically unobservable. However, the relaxation rates can be accounted for by the tilt angle between the molecular director and the layer normal in the SmC* phase. The tumbling motion appears to show a higher activation energy upon entering from the uniaxial SmA into the SmC* phase.     

Molecular models for ferroelectric liquid crystals with conventional and anomalously weak layer contraction

A molecular theory of the ferroelectric smectic C* phase has been developed using the simple model of a chiral molecule composed of a uniaxial core and a pair of off-center nonparallel dipoles which determine molecular chirality and polarity. The interaction between uniaxial cores is modeled by a rather general effective potential which can be used to describe smectic materials with both conventional and anomalously weak layer contraction in the smectic C* phase. Spontaneous polarization, tilt, and layer spacing are calculated numerically as functions of temperature, and it is shown that the variation of the polarization generally deviates from that of the tilt angle. It is shown that this deviation is more pronounced in smectic materials tilting with low layer contraction which corresponds to existing experimental data. The model has been used to reproduce qualitatively the experimental data for polarization, tilt and layer spacing for two similar mixtures exhibiting conventional and anomalously weak layer contraction. The polarization and the tilt are also calculated in the case when the smectic A-smectic C* transition is characterized by the biaxial primary order parameter.     

The effects of molecular shape and quadrupole moment on tilted smectic phase formation

Results are presented from constant NPT Monte Carlo simulations of two systems based on the biaxial internally rotated Gay-Berne (IRGB) potential. First, the effect of increasing molecular elongation is considered, and it is shown that a change in aspect ratio from 3:1 to 4:1 leads to nematic and tilted smectic J phases being replaced by smectic A and tilted smectic G phases, respectively. Second, the effect of a longitudinal electric quadrupole on the phase behaviour of the IRGB model is examined. The presence of a moderate quadrupole moment results in the smectic G phase being replaced by a smectic J; the onset pressure of the smectic J increases monotonically as the quadrupole moment is increased, although the integrity of the tilted layers improves. In addition, the region of smectic A stability is found to persist for moderate quadrupole moment values. For the largest quadrupole moment considered, domains comprising poorly defined, tilted layers are formed but fail to develop into coherent smectic structures. This observation is ascribed to the competition between the unique tilt direction favoured by the biaxial IRGB potential and the random tilt direction of the uniaxial quadrupole-quadrupole interactions.     

Dielectric spectroscopy of the SmQ* phase

Liquid crystal possessing two biphenyl moieties in the molecular core and lateral chlorine substitution far from the chiral chain has been studied by dielectric spectroscopy. On cooling from the isotropic phase, the material possesses the frustrated smectic Q* (SmQ*) and SmC_A* phases. It has been confirmed by dielectric spectroscopy that the SmQ* phase can be related to the SmC_A* anti-ferroelectric phase. However, only one relaxation process has been observed in the SmQ* phase, while in the SmC_A*, two relaxations are clearly detectable. It seems that the mode found in the SmQ* can be connected with high-frequency anti-phase mode observed in the SmC_A* phase. Its relaxation frequency is similar to P_H relaxation frequency, but is weaker. The same relaxation has been observed even a few degrees above the SmQ*–Iso phase transition. Another explanation for the mode detected in SmQ* and isotropic phases can be molecular motions around short molecular axis.