High strength disclinations in a rigid rod nematic polytolane

Transient disclinations of strength ± 3/2 were observed in the nematic phase of a single-component, thermotropic, rigid rod polytolane. These disclinations were characterized by 6 extinction brushes in textures observed by hot stage transmitted polarized light microscopy. The small number and short lifetime of these disclinations is discussed in terms of their energy per unit line length, and in terms of the force that causes them to be attracted to and annihilated at other disclinations.     

Wide nematic phases induced by hydrogen-bonding

New series of hydrogen-bonded supramolecular complexes, In/IIm, were prepared and investigated for their mesophase behaviour. The complexes were prepared through hydrogen-bonding between equimolar amounts of 4-alkoxyphenylazo-benzoic acids as the proton donors and non-mesomorphic 4-alkoxyphenylazo pyridines as the proton acceptors. The length of the terminal alkoxy chains was varied systematically on both terminals of the supramolecular complexes. The formation of 1:1 hydrogen-bonded complexes was confirmed by differential scanning calorimetry (DSC) and FTIR spectroscopy. All of new complexes were characterised by DSC and polarised light microscopy (PLM). It was found that the prepared complexes are dimorphic, possessing smectic C (SmC) and nematic (N) phases with relatively wide ranges. A comparison was made between the present series of complexes and the previously investigated isomers of the simple 4-alkoxybenzoic acids with the 4-(4?-pyridylazophenyl)-4??-alkoxybenzoates, revealed the stability of the nematic phase is dependent on the length of the acid component.     

High strength disclinations in the nematic and smectic states of 2,5-bis(4-alkoxybenzoyloxy)- p -benzoquinones

High strength disclinations were observed in both nematic and smectic phases exhibited by members of the 2,5-bis(4-alkoxybenzoyloxy)- p -benzoquinone series, beyond 4- n -pentoxy. The shorter members of the series show only a nematic mesophase, the highest members only a smectic mesophase, while intermediate members exhibit both types of mesophase. These high strength disclinations seen in a single component system are very stable due to energy dispersion and the high viscosity of the smectic state. All the high strength disclinations are negative in sign.     

Recent advances in the observation of disclinations of main-chain nematic polymers

Experimental observation of disclinations of main-chain nematic polymers is reviewed. The geometry of disclination structure is discussed both from observations of schlieren texture and the theory of curvature elasticity for a two-dimensional case with equal splay and bend moduli. The effects of non-equal elastic moduli, the nature of the disclination core and the observation of inversion wails are briefly mentioned. Examples of experimental observation of disclinations of high topological strengths up to S=4 are given. The main experimental methods to map the director field around disclinations are 1) lamellar decoration, 2) band-texture decoration and 3) surface microcrack decoration. The methods are discussed and compared, and examples illustrated by electron micrographs or photomicrographs are presented.     

The identification of the sign and strength of disclinations in the schlieren (nucleated domain) texture of the nematic phase,by optical microscopy

ABSTRACT

The optical texture of the nematic phase, variously known as the schlieren, structure à noyuax or nucleated domain texture, was identified over a century ago as being an array of point singularities. When viewed between crossed polars, patterns of dark brushes radiate from each point nucleus. The sign and strength of each nucleus can be uniquely determined from the changes in the orientation of these brushes when either the sample or the crossed polars are rotated, from two formulae given by Chadrasekhar in 1977. However, these were given with little exemplification and have been largely overlooked. Consequently, the majority of the discussions given in current literature are either incomplete and confusing or, in some cases, incorrect. Here, we provide a detailed explanation of the textures and their behaviour as viewed with the most commonly used experimental geometry (i.e. with a rotating sample and stationary polars).     

Electroconvective dendrites in nematic phases having short range smectic order exhibited by the 4,n-alkoxybenzoic acids

Electroconvective (EC) dendrites (parabolic type) in nematic (N) liquid crystals with short range smectic order shown by 4,n-octyloxybenzoic acid (8-OBA) were observed. The driving of the dendrites by lateral d.c. and a.c. electric field parameters in the nematic temperature range was carried out. The dynamics of dendrite growth were studied and analysed by the Ivantsov two-dimensional solution for the diffusion equation. Using various combinations of blocked and unblocked electrodes, we studied dependences between the dimensionless electric field parameter and product of the dendrite parabolic radius and the velocity of the dendrite growth and found that the type of electrode significantly modifies these basic dependences. We attribute this effect possibly to the opposing ion propagation, i.e. gradient of electric field in direction opposite to that of the charge injection. A possible mechanism of EC dendrite growth is suggested. A comparison with thermal dendrites in liquid crystals is presented.     

Supramolecular assemblies of gold nanoparticles induced by hydrogen bond interactions

The formation of two-dimensional self-assemblies of ordered, packed gold nanoparticles is described. The nanoparticles were coated by a diamide thiol ligand (DASH) that ensured the connection of the nanoparticles through hydrogen bonds. The stability of the colloidal solutions is discussed with respect to the stability of the normal dodecanethiol-coated particles.     

Calorimetric study of the dissociation of the 3-carboxy pyridinium ion. The effect of the hydrogen bond on the base strength

A calorimetric study of the protonation of 3-carboxy pyridine is presented.The solute—solvent interactions (hydrogen bonds and dipoles), more so than the effects intrinsic to the molecule (the greater degree of s character in the hybrid molecular orbital containing the lone pair), seems to have the main influence on the protonation of pyridine in the liquid phase.     

Normal‐stress differences and the detection of disclinations in nematic elastomers

We used a continuum model to investigate the isochoric radial expansion of a right circular cylindrical specimen composed of a nematic elastomer that is crosslinked in a uniaxial state and then annealed. Numerical solutions show that, above a certain radial expansion, the material has a definitive energetic preference for a state involving a disclination of strength +1 along the cylinder axis. Surrounding such a disclination is a core with radial dimension on the order of 10^?2 μm, which coincides with observations in conventional liquid‐crystal melts. Examination of the normal‐stress differences indicates that the first of these differences depends nonmonotically on the extent of radial expansion and possesses a local minimum at the point where a disclination becomes energetically preferred. This suggests a practical experimental method for testing the predictions of our model. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2098–2106, 2002     

Influence of intramolecular hydrogen bond strength on OH-stretching overtones

Vapor-phase OH-stretching overtone spectra of 1,3-propanediol and 1,4-butanediol were recorded and compared to the spectra of ethylene glycol to investigate the effect of increased intramolecular hydrogen bond strength on OH-stretching overtone transitions. The spectra were recorded with laser photoacoustic spectroscopy in the second and third OH-stretching overtone regions. The room-temperature spectra of each molecule are dominated by two conformers that show intramolecular hydrogen bonding. Anharmonic oscillator local-mode calculations of the OH-stretching transitions have been performed to aid assignment of the different conformers in the spectra and to illustrate the effect of the intramolecular hydrogen bonding. The hydrogen bond strength increases in the order ethylene glycol, 1,3-propanediol, and 1,4-butanediol. The overtone transitions of the hydrogen-bonded hydroxyl groups are more difficult to observe with increasing intramolecular hydrogen bond strength. We suggest that the bandwidth of these transitions increases with increasing hydrogen bond strength and with increasing overtone and furthermore that these changes are in part responsible for the lack of observed overtone spectra for complexes.     

Estimation of O-H bond dissociation energies in alcohols and acids from kinetic data

The O-H bond dissociation energies (D _O-H) in five alcohols and six acids have been determined from experimental data (rate constants of radical reactions). The ratio of the rate constants of the reactions R¹O˙+RH→R¹OH+R˙ and R ⁱ O˙+RH→R ⁱ OH+R˙ and the intersecting parabolas method are used in the estimation procedure. The D _O-H values are used to calculate the activation energies and rate constants for hydrogen abstraction from 2-methylbutane, butene-1, and cumene by alkoxyl and carboxyl radicals. The geometric parameters of the transition state are calculated for these reactions.     

An explanation of the unusual strength of the hydrogen bond in small water clusters

We seek to explain why the hydrogen bond possesses unusual strength in small water clusters that account for many of the complex behaviors of water. We have investigated and visualized the donation of covalent character from covalent (sigma) to hydrogen bonds by calculating the eigenvector coupling properties of quantum theory of atoms in molecules (QTAIM), stress tensor σ ( r ), and Ehrenfest Force F ( r ) on the F ( r ) molecular graph. The next-generation three-dimensional (3-D) bond-path framework sets are presented, and only the F ( r ) bond-path framework sets reproduce the earlier finding on the coupling between covalent (sigma) and hydrogen bonds that possess a degree of covalent character. Exploration of the bond-path between the covalent (sigma) and hydrogen bond's critical points provides an explanation for the previously obtained coupling results. The directional character of the covalent (sigma) and hydrogen bonds' 3-D bond-path framework sets for the F ( r ) explains differences found in the earlier results from QTAIM and the stress tensor σ ( r ).     

Direct decoration of disclinations by solidification-induced band texture for a nematic side chain liquid crystalline polymer

For a nematic polymethacrylate side chain liquid crystalline polymer, g 154 N 298 I (°C), the solidification-induced band texture has been observed aligned along the disclination under a polarizing optical microscope, when the specimen was quenched from 280°C to room temperature. The decoration technique of solidification-induced band texture, which is usually reported for main chain liquid crystalline polymers, was then introduced to reveal the director field pattern along a disclination for this side chain liquid crystalline polymer. It was found by infra-red dichroism measurements that the director orientation is parallel with the direction of the band. On this basis, disclinations with strength s=±1/2 and s=±1 were mapped according to the corresponding pattern of solidification-induced band texture. In addition, two types of inversion wall, loop-like and splay-type walls, were also found to be decorated by the solidification-induced band texture.     

Relative strength of hydrogen bond interaction in alcohol–water complexes

Hydrogen binding energies are calculated for the different isomers of 1:1 complexes of methanol, ethanol and water using ab initio methods from MP2 to CCSD(T). Zero-point energy vibration and counterpoise corrections are considered and electron correlation effects are analyzed. In methanol–water and ethanol–water the most stable heterodimer is the one where the water plays the role of proton donor. In methanol–ethanol the two isomers have essentially the same energy and no favorite heterodimer could be discerned. The interplay between the relative binding energy is briefly discussed in conjunction with the incomplete mixing of alcohol–water systems.