Electrostatic Maxwell stress model of the shapes of condensed phase domains in monolayers at the air-water interface

The formation mechanism of the shapes of condensed phase domains in monolayers at the air-water interface was investigated taking into account the surface pressure, line tension, and electrostatic energy due to the spontaneous polarization generated in normal and in-plane direction. By deriving the shape equation of monolayer domains as the mechanical balance at the domain boundary, we found that the electrostatic energy contributes to the shape equation as electrostatic Maxwell stress. Development of a cusp from condensed phase domains of fatty acid monolayers, which has been experimentally observed, was analyzed by the shape equation. It was found that the development of a cusp originated from the strong Maxwell stress, which was induced by the non-uniform orientational distribution in the fatty acid domain, and that cusped shapes gave a minimum of the free energy of the domain. It demonstrates that the shape equation with Maxwell stress, which is derived in the present study, is useful to study the formation mechanism of the shapes of condensed phase domains in monolayers.     

Order electricity reconsidered

We have considered the Landau-de Gennes expansion of the distortion free energy to examine a possible connection between the electric polarization in terms of a gradient of the order parameter and the electric polarization resulting from splay and bend distortions of the director. In addition we have considered the electric polarization connected with the electric quadrupole density, which is not contained in the Landau-de Gennes expansion.     

Order electricity reconsidered

We have considered the Landau-de Gennes expansion of the distortion free energy to examine a possible connection between the electric polarization in terms of a gradient of the order parameter and the electric polarization resulting from splay and bend distortions of the director. In addition we have considered the electric polarization connected with the electric quadrupole density, which is not contained in the Landau-de Gennes expansion.     

The effect of the polarization electric field on helix-unwinding in a planar chiral smectic C liquid-crystal cell

The effect of the polarization electric field on helix-unwinding in a thin planar chiral smectic C liquid-crystal cell is studied by using the nematic-like expression for the elastic deformation free-energy density. It is found that the elongation of the helical pitch when the cell thickness decreases is greater when the spontaneous polarization is larger. This is due to the Coulomb repulsion between polarization charges concentrated at ± 2π disclinations.     

The effect of the polarization electric field on helix-unwinding in a planar chiral smectic C liquid-crystal cell

The effect of the polarization electric field on helix-unwinding in a thin planar chiral smectic C liquid-crystal cell is studied by using the nematic-like expression for the elastic deformation free-energy density. It is found that the elongation of the helical pitch when the cell thickness decreases is greater when the spontaneous polarization is larger. This is due to the Coulomb repulsion between polarization charges concentrated at ± 2π disclinations.     

Spontaneous Chirality Induction in the Assembly of a Single Layer 2D Network with Switchable Pores

Although two-dimensional (2D) chiral sheet structures are attractive because of their unique chemical and physical properties, single layer 2D chiral network structures with switchable pore interior remain elusive. Here we report spontaneous chirality induction in a single layer 2D network structure formed from the self-assembly of tetrapod azobenzene molecules. The chirality induction arises from multiple sublayers slipped in a preferred direction in which the sublayer consists of unidentical molecular arrangements in the in-plane a and b directions, breaking both the plane of symmetry and inversion symmetry. The protruded azobenzene units in the pore interior can be selectively isomerized upon UV irradiation, resulting in a reversible deformation of the chiral pores while maintaining the 2D frameworks. The chiral network can thus selectively entrap one enantiomer from a racemic solution with near perfect enantioselectivity, and then release it upon UV irradiation.     

Direct chiral discrimination in NMR spectroscopy

Conventional nuclear magnetic resonance spectroscopy is unable to distinguish between the two mirror-image forms (enantiomers) of a chiral molecule. This is because the NMR spectrum is determined by the chemical shifts and spin–spin coupling constants which – in the absence of a chiral solvent – are identical for the two enantiomers. We discuss how chirality may nevertheless be directly detected in liquid-state NMR spectroscopy: In a chiral molecule, the rotating nuclear magnetic moment induces an electric dipole moment in the direction perpendicular to itself and to the permanent magnetic field of the spectrometer. We present computations of the precessing electric polarization following a π/2 pulse. Our estimates indicate that the electric polarization should be detectable in favourable cases. We also predict that application of an electrostatic field induces a chirally sensitive magnetization oscillating in the direction of the permanent magnetic field. We show that the electric-field-perturbed chemical shift tensor, the nuclear magnetic shielding polarizability, underlies these chiral NMR effects.     

Direction-dependent circular dichroism spectra of single crystals of cubic sodium uranyl acetate

The contribution of the electric quadrupole mechanism to the chirality of optically active cubic sodium uranyl acetate single crystals has been established by measurements of the direction dependence of circular dichroism spectra. The CD bands for Σ_g⁺→Δ_g transitions are found to be direction dependent while those for Σ_g⁺→Π_g are direction-independent for light propagation k parallel to the (100) and (111) directions of the cubic cell. The contribution of the electric quadrupole mechanism to the chirality relative to that of the magnetic dipole mechanism is estimated to be about 20%.     

Quasi chiral phase separation in a two-dimensional orientationally disordered system: 6-nitrospiropyran on Au(111)

The adsorption and chiral expression of 6-nitrospiropyran (SP6) molecules on a Au(111) surface are studied by scanning tunneling microscopy (STM) in combination with density functional theory (DFT) calculations. Both the chirality and the adsorption orientation of each adsorbed SP6 molecule are determined. The racemic mixture of SP6 enantiomers forms two-dimensional (2D) domains with same close packed positional orders but different internal orientational structures due to the random distribution of two adsorption orientations in each domain. However, all these orientationally disordered 2D domains undergo spontaneous quasi chiral phase separation; the 2D SP6 domains separate into 1D homochiral chains in which the SP6 molecules adopt two orientations randomly. This novel phenomenon is attributed to the preferential formation of the energetic favorable configurations with both the C-H...O weak hydrogen bonds and the pi-stacking of the two moieties of each SP6 molecule.     

Tilt and temperature dependence of the pitch in the chiral smectic C phase

The chirality of the constituent molecules in the chiral smectic phase induces a helical structure with a pitch, p₀. Because of the tilt and chirality there is a spontaneous polarization and a bend deformation which act upon the induced helix. The resulting pitch is described as a function of p₀ using the phenomenological theory of a chiral smectic C phase. The pitch, p₀, is then calculated using a molecular theory of the cholesteric phase. The results obtained explain the experimental observations, at least qualitatively.     

Magnitude and direction of the spontaneous polarization of ferroelectric liquid crystals with several bond moments

The magnitude and direction of the spontaneous polarization in most ferroelectric liquid crystals have been confirmed to be determined by the location and magnitude of the bond moment around the chiral carbon and the core. In compounds with several bond moments their relative orientation is very important for obtaining a large spontaneous polarization. Compounds with benzene rings in the core substituted with OH also have a large spontaneous polarization, perhaps due to the formation of hydrogen bonds. Reversal of the direction of the spontaneous polarization with temperature has been found for EFPPOPB. This anomalous behaviour has been explained tentatively in terms of a conformation change due to the existence of a flexible -CH₂- unit between the chiral carbon and the dipole moment.     

The effect of pretransitional phenomena on the characteristics of induced ferroelectric liquid-crystalline systems

The effect of different types of phase transition on the temperature dependence of the helical pitch and the spontaneous polarization is investigated for mixtures of smectic C liquid crystals and a chiral dopant, based on salicylidenanylene derivatives. The observed phenomena are explained by assuming that the temperature dependence of the pitch is connected with the growth of the disclination loops near the second order phase transition, and that the subsurface electric field can unwind the helix in chiral substances with strong piezoelectric effects which occur for large polarization values.     

The effect of pretransitional phenomena on the characteristics of induced ferroelectric liquid-crystalline systems

The effect of different types of phase transition on the temperature dependence of the helical pitch and the spontaneous polarization is investigated for mixtures of smectic C liquid crystals and a chiral dopant, based on salicylidenanylene derivatives. The observed phenomena are explained by assuming that the temperature dependence of the pitch is connected with the growth of the disclination loops near the second order phase transition, and that the subsurface electric field can unwind the helix in chiral substances with strong piezoelectric effects which occur for large polarization values.     

Magnitude and direction of the spontaneous polarization of ferroelectric liquid crystals with several bond moments

The magnitude and direction of the spontaneous polarization in most ferroelectric liquid crystals have been confirmed to be determined by the location and magnitude of the bond moment around the chiral carbon and the core. In compounds with several bond moments their relative orientation is very important for obtaining a large spontaneous polarization. Compounds with benzene rings in the core substituted with OH also have a large spontaneous polarization, perhaps due to the formation of hydrogen bonds. Reversal of the direction of the spontaneous polarization with temperature has been found for EFPPOPB. This anomalous behaviour has been explained tentatively in terms of a conformation change due to the existence of a flexible -CH₂- unit between the chiral carbon and the dipole moment.     

The influence of chirality on the difference in flexoelectric coefficients investigated in uniform lying helix,Grandjean and twisted nematic structures

Measurements of the difference in flexoelectric coefficients (e ₁ – e ₃), using the sign convention as originally defined by Meyer, are reported from three experiments employing the flexoelectro-optic effect in different geometries. The uniform lying helix (ULH) structure is used to measure the tilt angle of the liquid crystal director with respect to the helix axis for an applied electric field, in order to infer a value for (e ₁ – e ₃). Alternatively, measurements of the flexoelectric difference can be made by considering the transmission through a device with an in-plane electric field aligned in either the Grandjean structure for highly chiral materials, or a twisted nematic (TN) structure for largely achiral materials. The results from the Grandjean and ULH structures show the equivalence of the measurement techniques with helix axis either perpendicular or parallel to the substrates. Further comparison of these results with the measurement from the achiral TN device shows that the difference in flexoelectric coefficients displays no dependence on chirality, demonstrating that flexoelectricity is purely associated with splay and bend director deformations, as expected from symmetry considerations.     

Superpositions of chiral states in the presence of electric dipole, magnetic dipole, and electric quadrupole interactions

This paper is a straightforward generalization of Maierle-Harris proposal regarding parity implications on the superpositions of chiral states of a molecule. It is shown that the inclusion of electric quadrupole and magnetic dipole interactions removes several of restrictions on the preparation of superpositions of mid R:L and mid R:R states of a chiral molecule. It is also found that the dephasing of mid R:L and mid R:R superpositions, due to the spontaneous emission from the chiral molecule, has opposing contributions from electric quadrupole-magnetic dipole and electric dipole interactions.     

Fast-switching ferrolectric liquid crystalline polymers containing one or two centres of chirality in the side chain

In a liquid crystalline side chain polyacrylate containing one center of chirality in the terminal alkyl chain of the mesogenic part, switching times of 200–400 μs were measured in the SmC^* phase. Below this phase an unidentified phase exists, which shows electroclinic-like switching. The phase transition between those two phases can be shifted by applying an electric field. At higher molecular weights three subphases emerge in the SmC^* region. Variation of the spacer length revealed, for the first time, ferroelectric switching even at a spacer length of only two CH₂ groups. By shifting the centre of chirality into the spacer of the side group a polymer resulted, which shows electroclinic switching in the SmC^* phase, changing to ferroelectric switching when the voltage is increased. Incorporation of an oxirane ring as chiral building block into the spacer yielded a polymer that shows a sign inversion of the spontaneous polarization in the SmC^* phase. A polymer containing a dioxolane carbonic ester as chiral unit exhibits three switching states, with the third state existing at a low or zero electric field. This phenomenon is known for antiferroelectric liquid crystals. By doping a racemic LC polymer with a chiral monomeric LC we induced a spontaneous polarization. Colored FLC polymers were obtained by two different approaches. In an FLC–dye copolymer, increasing switching speed in three different chiral smectic phases was observed when increasing the dye concentration.     

Collective interactions in the mechanism of adhesion of condensed phase nuclei to a crystal surface. 1. Spatial organization

Self-organization into domains with spontaneous polarization is revealed for an ensemble of water molecules occurring in a contact layer on a defectless polarizable crystal surface. These domains are the sources for specific heteropolarization interactions of condensed phase nuclei with a substrate. The formation of a spatially nonuniform structure is energetically advantageous due to a nonlinear dependence of polarization energy on field strength. Domain sizes equal to several nanometers are governed by the competition between the energy advantage resulting from the coalescence of the domains and the entropy gain caused by their disintegration into smaller fragments. The forces of spontaneous mutual polarization between an adsorbed film divided into domains and a polarized substrate enhance the adhesion to the surface and markedly affect the adsorption mechanism. Computer simulation of the domain formation in a film of water molecules adsorbed on the surface of crystalline silver iodide particles is implemented by the Monte Carlo method with the summation of the long-range electrostatic interactions by means of the Fourier expansion of the field potential. Comparative analysis of the collective behavior of molecules, which underlies the layer-by-layer nucleation, and the indirect signs of domain formation is performed on the basis of experimental data on polarized surfaces with a hexagonal crystalline structure.     

Light-induced Freedericksz transition in a nematic liquid crystal with chiral dopant

The influence of phototransformed molecules with chiralproperties changing on the absorption of light field on the light-induced Freedericksz transition threshold in a homeotropically oriented nematic cell is considered. It is shown that the appearance of the light-induced chiral molecules can decrease or increase the Freedericksz threshold value depending on the chirality sign of the phototransformed molecules and of the initial chiral dopant. Expressions for the threshold are obtained for circular and linear polarization of the incident light. The dependence of the threshold on the periodicity of the spatially modulated light intensity is estimated for large periods of modulation. The dependence of dopant threshold chirality on the director anchoring energy has been found.     

Ferroelectric properties of smectic C liquid crystals with induced helical structure

Ferroelectricity has been observed in liquid crystalline mixtures of chiral smectic C type with a helical structure induced by chiral guest molecules (pitch p ≈ 100 μm). Samples of thickness d?p form monodomains with finite zero-field electric polarization because the spontaneous polarization of the smectic layers is not compensated by the helical twist. The temperature dependence of the spontaneous polarization has been studied near the phase transition smectic C→ smectic A.