Smectic-isotropic Transition Research Articles

Phase transitions of smectic-isotropic phase in liquid crystals

Smectic phases formed by rod-like molecules with long axes that are parallel and also arranged in planes. The smectic-isotropic phase transition is a phase change from the liquid crystal to the liquid phase. In this work, we use a mobile 6-state Potts model to study the nature of the smectic-isotropic phase transition. Microscopic interactions between neighbouring molecules in this model are supplemented with the Lennard-Jones potential. This study applies Monte Carlo simulation with the Wang-Landau algorithm to determine the characteristics of smectic-isotropic phase transitions. It is shown clearly that the smectic phase goes to the isotropic phase and undergoes a first-order transition. The results also point out that when the temperature increases, molecules on the surface are orientationally disordered, then the molecules gradually lose their positional order. These results are in agreement with experiments that revealed the coexistence of the smectic and isotropic phasesduring the phase transition process in accordance with experimental studies.

The influence of the imine bond direction on the phase behaviour of symmetric and non-symmetric liquid crystal dimers

The synthesis and characterisation of two series of liquid crystal dimers are reported: the symmetric 1,5-bis(4′-oxyanilinebenzylidene-4-alkane)pentanes (m-O5O-m), and the non-symmetric 1-(4-cyanobiphenyl-4′-yloxy)-5-(4′-oxyanilinebenzylidene-4-alkane)pentanes (CBO5O-m). In the acronyms for each series m refers to the terminal chain length. The m-O5O-m series showed monotropic nematic phases for m = 1-7. Smectic behaviour emerged at m = 7 and nematic behaviour extinguished at m = 8. For the CBO5O-m series, an enantiotropic nematic phase is seen for m = 1-10. In addition, m = 1 shows a twist-bend nematic phase, and m = 9 and 10 an interdigitated smectic A phase. These series are compared to the corresponding dimers in which the imine link in the benzylideneaniline fragments is reversed, the m.O5O.m and CBO5O.m series. For the symmetric dimers, reversing the imine link has a small effect on the nematic-isotropic transition temperatures, TNI, but a much larger effect on the smectic-isotropic transition temperatures, TSmI. In both cases, the m.OnO.m series shows the higher values. The values of TNI are also slightly higher for the CBO5O.m series than the CBO5O-m series. Surprisingly, the values of TSmI are higher for the CBO5O-m than for the CBO5O.m series. These differences are discussed in terms of the changes in shape and electronic distributions arising from reversing the imine link.

Circulating Marangoni flows within droplets in smectic films.

We present a theoretical study and numerical simulation of Marangoni convection within ellipsoidal isotropic droplets embedded in free-standing smectic films (FSSFs). The thermocapillary flows are analyzed for both isotropic droplets spontaneously formed in FSSF overheated above the bulk smectic-isotropic transition and oil lenses deposited on the surface of the smectic film. The realistic model for which the upper drop interface is free from the smectic layers, while at the lower drop surface the smectic layering persists is considered in detail. For isotropic droplets and oil lenses this leads effectively to a sticking of fluid motion at the border with a smectic shell. The above mentioned asymmetric configuration is realized experimentally when the temperature of the upper side of the film is higher than at the lower one. The full set of stationary solutions for Stokes stream functions describing the Marangoni convection flows within the ellipsoidal drops are derived analytically. The temperature distribution in the ellipsoidal drop and the surrounding air is determined in the frame of the perturbation theory. As a result, the analytical solutions for the stationary thermocapillary convection are obtained for different droplet ellipticity ratios and the heat conductivity of the liquid crystal and air. In parallel, the numerical hydrodynamic calculations of the thermocapillary motion in drops are made. Both analytical and numerical simulations predict the axially symmetric circulatory convection motion determined by the Marangoni effect at the droplet-free surface. Due to a curvature of the drop interface a temperature gradient along its free surface always exists. Thus, the thermocapillary convection within the ellipsoidal droplets in overheated FSSF is possible for the arbitrarily small Marangoni numbers. Possible experimental observations enabling the checking of our predictions are proposed.

Giant electrocaloric response in smectic liquid crystals with direct smectic-isotropic transition

Electrocaloric materials have become a viable technology for solid state heat management applications. We demonstrate both theoretically and experimentally that liquid crystals (LCs) can be exploited as efficient electrocaloric materials. Numerical and experimental investigations determine the conditions under which the strongest electrocaloric effect (ECE) responses are expected in LCs. Specifically, we show that a large ECE can be expected at the isotropic-nematic and in particular at the isotropic-smectic A phase transition. In our theoretical study, LC ordering is modelled using a Landau – de Gennes - Ginzburg mesoscopic approach. The simulation results are in qualitative agreement with our high precision electrocaloric measurements conducted on 8CB and 12CB liquid crystals. In the latter, we obtained ΔTEC ~ 6.5 K, corresponding to the largest response measured so far in LCs. The fluid property of LC electrocaloric heat cooling elements could lead to the development of devices with a higher coefficient of performance and thus better cooling power yield per mass of the ECE-based device.

7-Hexyloxy-3-[4’-(3-methylbutyloxy) phenyl]-4H-1-benzopyran-4-one: Study of Smectic behaviour and UV absorption profile

abstractThe intermolecular interaction energies between a pair of 7-Hexyloxy-3-[4’-(3-methylbutyloxy) phenyl]-4H-1-benzopyran-4-one (HMBPB) molecules have been estimated with respect to translational and orientational motions. The complete neglect differential overlap (CNDO/S) method has been employed to calculate the net atomic charge and atomic dipole moment components at each atomic center. The modified Rayleigh-Schrodinger perturbation theory along with multicentered-multipole expansion method has been employed to evaluate the long-range intermolecular interactions, while a ‘6-exp’ potential function has been assumed for short-range interactions. The total interaction energy values obtained through these computations have been used to calculate the probability of each configuration at room temperature (300K), and isotropic-smectic transition temperature (412.6K). Molecular arrangements inside a bulk of materials and smectic behavior of the compound in terms of their relative order have been discussed. Translational and rotational rigidity of the molecule has been analyzed to understand the smectic behaviour. The UV absorption profile has been estimated using CNDO/S, and INDO/S methods.

Photocontrollable Self-Assembly of Azobenzene-Decorated Nanoparticles in Bulk: Computer Simulation Study

Decoration of nanoparticles by specific functional groups provides means of controlling their aggregation and self-assembly into ordered morphologies. We study the photocontrollable self-assembly of the azobenzene-functionalized nanoparticles using coarse-grained molecular dynamics simulations. With no illumination applied, a monodomain smectic morphology is formed only via cooling the isotropic system at a sufficiently slow rate. Quenching the system below the smectic–isotropic transition results in formation of a polydomain glass-like state with restricted dynamics of nanoparticles. Upon irradiation with appropriate wavelength and intensity, the azobenzenes undergo trans–cis–trans photoisomerization cycles which unlock the interdomain links and induce uniaxial orientation of domains with their local director perpendicular to the polarization axis of irradiation. As demonstrated by the simulations, this transition can speed up essentially the self-assembly of decorated nanoparticles from the isotropic to the monodomain smectic phase, both via gradual cooling down and via quenching in a broad temperature interval below the smectic–isotropic transition.

Vitrification and plastic flow in transient elastomer networks

We investigate how the crossover temperature of the elastic-plastic transition, the ‘vitrification point’ Tv, changes under load for isotropic vitrimers and exchangeable liquid crystal elastomers (xLCEs), using the thermoplastic SIS triblock polymer as a reference. In all these cases, the elastic network cross-links are transient: physical micro-phase separation in SIS and covalent transesterification bonds in vitrimers. From the analysis of SIS we define Tv as the point when entropic rubber-elasticity contraction due to heating under load turns into the irreversible plastic extension due to cross-links breaking and reforming. In xLCEs, the response to mechanical stress is heavily influenced by the smectic liquid-crystalline order, which makes the material much stiffer than normal rubbery networks, and also leads to the shape-memory effect across the smectic-isotropic transition point. The vitrification in the isotropic phase of xLCE, and in isotropic vitrimers, was found to be independent of stress, which can be attributed to the thermal activity of the catalyst determining Tv and it not being mechanically coupled to the elastic network. Beyond Tv, with increasing stress the plastic extension rapidly increases with temperature, as cross-link dynamics becomes more apparent.

Simple theory of transitions between smectic, nematic, and isotropic phases.

The transitions between smectic, nematic, and isotropic phases are investigated in the framework of a unified molecular-statistical approach. The new translational order parameter is different from the one introduced in K. Kobayashi [Phys. Lett. A 31, 125 (1970)] and W. L. McMillan [Phys. Rev. A 4, 1238 (1971)]. The variance of the square sine of intermolecular shift angle along the director is introduced to take self-consistently into account the most probable location of the molecules with respect to each other, which is unique for every liquid crystal (LC) material and is mainly responsible for the order parameters and phase sequences. The mean molecular field was treated in terms of only two parameters specific to any intermolecular potential of elongated molecules: (1) its global minimum position with respect to the shift of two interacting molecules along the director and (2) its inhomogeneity/anisotropy ratio. A simple molecular model is also introduced, where the global minimum position is determined by the linking groups elongation Δ/d, while the inhomogeneity/anisotropy ratio Gβ/Gγ is determined by the ratio of electrostatic and dispersion contributions. All possible phase sequences, including abrupt/continuous transformation between the smectic and nematic states and the direct smectic-isotropic phase transition, are predicted. The theoretical prediction is in a good agreement with experimental data for some simple materials correlating with our molecular model, but it is expected to be valid for any LC material.

Dependence of Mesomorphism on Molecular Rigidity

A novel smectogenic homologous series of twelve homologues synthesized and studied with a view to understand and establish the effect of molecular structure on liquid crystal properties (LC) and LC behaviors of thermotropic homologues. First (C1) to last (C16) member of a series exhibited only enantiotropically smectogenic property without showing nematic property which is absent even in the monotropic condition. Transition and melting temperature including textures of homologues were determined by an optical polarizing microscopy equipped with a heating stage, texture of a smectic phase are of the type A or C. Smectogenic phase length ranger between 5.1°C to 22.6°C. Smectic-Isotropic (Sm-I) thermal stability is 153.55°C. Analytical, spectral and thermal data supported molecular structures of homologues. LC behaviors of present novel series are compared with the structurally similar homologous series. Transition curves viz. Cr-Sm and Sm-I transition curves of a phase diagram behaved in normal manner.

Dependence of Mesomorphism on Molecular Rigidity

A novel smectogenic homologous series of twelve homologues synthesized and studied with a view to understand and establish the effect of molecular structure on liquid crystal properties (LC) and LC behaviors of thermotropic homologues. First (C1) to last (C16) member of a series exhibited only enantiotropically smectogenic property without showing nematic property which is absent even in the monotropic condition. Transition and melting temperature including textures of homologues were determined by an optical polarizing microscopy equipped with a heating stage, texture of a smectic phase are of the type A or C. Smectogenic phase length ranger between 5.1°C to 22.6°C. Smectic-Isotropic (Sm-I) thermal stability is 153.55°C. Analytical, spectral and thermal data supported molecular structures of homologues. LC behaviors of present novel series are compared with the structurally similar homologous series. Transition curves viz. Cr-Sm and Sm-I transition curves of a phase diagram behaved in normal manner.

Transition Helmholtz free energy, entropy, and heat capacity of free-standing smectic films in water: a mean-field treatment.

Using the extended McMillan's mean field approach with anisotropic forces a study of both the structural and thermodynamic properties of free-standing smectic film (FSSF) in water on heating to the isotropic temperature is carried out numerically. By solving the self-consistent nonlinear equations for the order parameters, we obtained that the smectic-A-isotropic (AI) transition occurs through the series of layer-thinning transitions causing the films to thin in the stepwise manner as the temperature is increased above the bulk smectic-A-isotropic temperature TAI(bulk). With enhanced pair interactions in the bounding layers, the smectic-isotropic transition corresponds to smectic melting of the central layers. The effects of surface "enhanced" pair interactions in the bounding layers and of film thickness on the orientational and translational order parameters, the Helmholtz free energy and entropy, as well as the temperature dependence of the heat capacity of FSSFs, have also been investigated. Reasonable agreement between the theoretically predicted and the experimentally obtained - by means of optical microscopy and ellipsometry techniques - data of the temperature when the thin decylcyanobiphenyl smectic film immersing in water ruptures has been obtained.

Photoresponsive Smectic Liquid Crystalline Multipods and Hyperbranched Azo Polymers

Liquid crystalline azobenzene containing triped and tetraped monomers were designed and synthesized and further used as B3 and B4 type monomers to form hyperbranched polymers with tetraethylene glycol as the A2 type comonomer. The mesophase characteristics of the multiarm-star mesogens and hyperbranched polymers were analyzed using various instrumentation techniques like differential scanning calorimetry (DSC), polarized light microscopy (PLM) and variable temperature XRD. The multipod monomers as well as hyperbranched polymers exhibited thermotropic smectic liquid crystalline characteristics with a tendency toward higher ordered smectic LC phases with increased branching. The hyperbranched polymers exhibited lamellar organization even in the as-solvent precipitated powder sample indicating higher extent of nanosegregation. Their potential application as fast switching photochromic materials was highlighted by carrying out isothermal photoswitching experiments in the LC state. Reversible isothermal smectic-isotropic phase transition could be achieved by UV irradiation in <1 s in the multipod monomers, while it required >2 s UV irradiation in the case of the hyperbranched polymers.

The Smectic–Isotropic Transition of P3HT Determines the Formation of Nanowires or Nanotubes into Porous Templates

We present the simple and controllable fabrication of ordered arrays of poly(3-hexylthiophene) (P3HT) solid nanowires and hollow nanotubes by infiltrating the molten polymer into AAO nanopores at temperatures promoting partial (260 °C) and complete (280 °C) wetting regimes, respectively. We show that such wetting regimes (and thus the formation of nanowires or nanotubes) are associated with a different internal structure in the P3HT melt. At 260 °C, the P3HT organizes into a smectic mesophase. Thus, the translational motion of the P3HT molecule through the phase-separated structure would involve an enthalpic penalty, which prevents the molecular diffusion required for achieving the complete wetting regime. Consequently, the P3HT wets the nanopores in partial wetting regime, so that solid nanowires are formed. In contrast, the melt is structurally isotropic at 280 °C, which promotes the complete wetting regime, yielding nanotubes. Such a smectic mesophase is also present in P3HT confined into 350 nm in dia...

Liquid‐Crystalline Elastomer‐Nanoparticle Hybrids with Reversible Switch of Magnetic Memory

A stimuli-responsive material is synthesized that combines the actuation potential of liquid-crystalline elastomers with the anisotropic magnetic properties of ellipsoidal iron oxide nanoparticles. The resulting nanocomposite exhibits unique shape-memory features with magnetic information, which can be reversibly stored and erased via parameters typical of soft materials, such as high deformations, low stresses, and liquid-crystalline smectic-isotropic transition temperatures.

Molecular Structure and Ordering in a Fluorinated Smectogenic Compound—A Statistical Thermodynamic Approach

In the present paper, molecular structure and ordering in a fluorinated smectogenic compound 4-propyloxyphenyl 4-(4-trifluoromethyl-benzoyloxy) benzoate (FLUORO) with respect to translatory and orientational motions have been reported. The evaluation of net atomic charges and dipole moments at each atomic center has been carried out through the complete neglect differential overlap (CNDO/2) method. The modified Rayleigh–Schrodinger perturbation method along with multicentered-multipole expansion method has been employed to evaluate the long-range intermolecular interactions, while a “6-exp” potential function has been assumed for the short-range interactions. The total interaction energy values obtained through these computations have been used to calculate the probability of each configuration at room temperature (300 K), smectic–isotropic transition temperature (488 K), and above transition temperature (550 K) using the Maxwell–Boltzmann formula. Further, thermodynamic parameters such as Helmholtz free energy and entropy have been computed during the different modes of interactions. An attempt has been made to understand the phase behavior and ordering of the compound based on the thermodynamic parameters introduced in the paper.

Synthesis and Study of Novel Liquid Crystalline Homologous Series: 4-(4′-n-Alkoxy Benzoyloxy)-3-Methoxy Phenyl azo-3″, 4″ Dichlorobenzenes

The synthesis and mesomorphic properties of a new homologous series of azomesogens, 4-(4′-n-alkoxy benzoyloxy)-3-methoxy phenyl azo-3″,4″ dichlorobenzene is detailed. The first four members of the series are nonmesomorphic, and the other eight members are smectogenic in character. The smectic mesophase, which is exhibited montropically, commences from the pentyl to the hexadecyl derivatives. The usual odd-even effect is observed in the isotropic-smectic transition curve. The isotropic-smectic transition curve behaves in a normal manner. The smectic mesophase shows a focal conic fan shaped texture of the smectic A type. An important feature of the series is the absence of the nematic property. The thermal stability and mesomorphic characteristic are compared with two structurally similar homologous series.

Derivation of Coarse Grained Models for Multiscale Simulation of Liquid Crystalline Phase Transitions

We present a systematic derivation of a coarse grained (CG) model for molecular dynamics (MD) simulations of a liquid crystalline (LC) compound containing an azobenzene mesogen. The model aims at a later use in a multiscale modeling approach to study liquid crystalline phase transitions that are (photo)induced by the trans/cis photoisomerization of the mesogen. One of the major challenges in the coarse graining process is the development of models that are for a given chemical system structurally consistent with for example an all-atom reference model and reproduce relevant thermodynamic properties such as the LC phase behavior around the state point of interest. The reduction of number of degrees of freedom makes the resulting coarse models by construction state point dependent; that is, they cannot easily be transferred to a range of temperatures, densities, system compositions, etc. These are significant challenges, in particular if one wants to study LC phase transitions (thermally or photoinduced). In the present paper we show how one can systematically derive a CG model for a LC molecule that is highly consistent with an atomistic description by choosing an appropriate state point for the reference simulation. The reference state point is the supercooled liquid just below the smectic-isotropic phase transition which is characterized by a high degree of local nematic order while being overall isotropic. With the resulting CG model it is possible to switch between the atomistic and the CG levels (and vice versa) in a seamless manner maintaining values of all the relevant order parameters which describe the smectic A (smA) state. This model will allow us in the future to link large length scale and long time scale CG simulations of the LC state with chemically accurate QM/MM simulations of the photoisomerization process.

Estimation of Configurational Probability and Phase Behaviour of N-n-undecyl-D-gluconamide having V-Shaped Conformation – A Molecular Simulation Approach

The present article deals with the configurational probabilities of a smectogen N-n-undecyl-Dgluconamide (GAM11). The complete neglect differential overlap (CNDO/2) method has been employed to compute the net atomic charge and atomic dipole moment components at each atomic center. The modified Rayleigh-Schr¨odinger perturbation theory along with the multicentered-multipole expansion method has been employed to evaluate the long-range intermolecular interactions, while a ‘6-exp’ potential function has been assumed for short-range interactions. The total interaction energy values obtained during different modes of molecular interactions have been used as input to calculate the configurational probability at room temperature (300 K), and smectic-isotropic transition temperature (429:7 K) using the Maxwell-Boltzmann formula. The various possible geometrical arrangements of molecular pairs have been considered. Further, an attempt has been made to explain the smectic behaviour of GAM11 in terms of their relative order based on the molecular parameters introduced in this paper

Modelling elasticity and memory effects in liquid crystalline elastomers by molecular dynamics simulations

We performed molecular dynamics simulations of a liquid crystal elastomer of side-chain architecture. The network is formed from a melt of 28 molecules each having a backbone of 100 hydrocarbon monomers, to which 50 side chains are attached in a syndiotactic way. Crosslinking is performed in the smectic A phase. We observe an increase of the smectic–isotropic phase transition temperature of about 5 degrees as compared to the uncrosslinked melt. Memory effects in liquid crystalline order and in sample shape are well reproduced when the elastomer is driven through the smectic–isotropic transition. Above this transition, in the isotropic phase, the polydomain smectic phase is induced by a uniaxial load. Below the transition, in a monodomain smectic A phase, both experimentally observed effects of homogeneous director reorientation and stripe formation are reproduced when the sample is stretched along the director. When the load is applied perpendicularly to the director, the sample demonstrates reversible deformation with no change of liquid crystalline order, indicating elasticity of the two-dimensional network of polymer layers.

Surface ordering and anchoring behaviour at liquid crystal surfaces laden with semifluorinated alkane molecules

We study the surface ordering and anchoring behaviour at liquid crystal/air interfaces laden with the semifluorinated alkane C18H37–C12F25. On alkanes, the semifluorinated alkane is known to form Gibbs films exhibiting a sharp transition from a dilute state at higher temperatures to a dense state at lower temperatures. We observe a similar transition in Gibbs films of this compound on the surface of cyanobiphenyl liquid crystals. The transition temperature can be tuned by controlling the C18H37–C12F25 concentration in the liquid crystal bulk phase. Our results show that the transition in the Gibbs film changes the anchoring of the liquid crystal from homeotropic at higher temperatures to planar at lower temperatures. When the transition temperature of the Gibbs film is tuned so that it takes place above the nematic–isotropic or smectic–isotropic transition of the liquid crystals, a pronounced effect on the nematic or smectic surface order is observed. Our study demonstrates for the first time that the ordering and anchoring behaviour of thermotropic liquid crystals can be tuned at a liquid crystal/air interface.