Field dependence of the optical activity of a chiral liquid crystal near the isotropic–smectic A transition

Abstract

Chiral liquid crystals exhibit molecular optical activity in the isotropic phase. We have studied the evolution of the optical activity as a function of an applied electric field on a 76·2 μm film of the chiral liquid crystal W7, which exhibits an isotropic–smectic A transition at approximately 40°C. We measured the optical activity by recording the rotation of the plane of polarization of an incident linearly polarized ray of light, provided by a He–Ne laser. The applied biasing electric field is parallel to the direction of the incident beam. We find that at 41·0°C, the plane of polarization shifts from ?1·1° for an applied voltage of 30 V to a maximum of ?4·0° at 70 V. The absolute value of the signal decreases beyond this voltage. These shifts are in the direction of the smectic A phase and are in general larger than those observed as a function of temperature. Close to the isotropic–smectic A phase transition, molecules inside the liquid coalesce to form dynamic coherent groups, which have smectic nature. These groups are randomly oriented with respect to each other in the absence of an electric field. The application of an electric field causes the molecules within these groups to align along the direction of the field and to contribute coherently to the optical activity of the system. The way the molecules align with the field depends on the relative values of the polarizability α, which contributes to the alignment of the long axis of the molecule, and the dipole moment p, which contributes to the alignment of the short axis of the molecule. Our preliminary results and calculations suggest that for small fields, the electric field couples with the dipole moment p, whereas for fields in excess of 70 V, the field couples with the polarizability of the long axis of the molecule, causing a rotational reorientation of the molecules in the isotropic phase. The value of the field at which this reorientation occurs may be controlled by temperature.     

Measuring polarizability anisotropies of rare gas diatomic molecules by laser-induced molecular alignment technique

The polarizability anisotropies of homonuclear rare gas diatomic molecules, Ar(2), Kr(2), and Xe(2), are investigated by utilizing the interaction of the induced electric dipole moment with a nonresonant, nanosecond laser pulse. The degree of alignment, which depends on the depth of the interaction potential created by the intense laser field, is measured, and is found to increase in order of Ar(2), Kr(2), and Xe(2) at the same peak intensity. Compared with a reference I(2) molecule, Ar(2), Kr(2), and Xe(2) are found to have the polarizability anisotropies of 0.45 ± 0.13, 0.72 ± 0.13, and 1.23 ± 0.21 A?(3), respectively, where the uncertainties (one standard deviation) in the polarizability anisotropies are carefully evaluated on the basis of the laser intensity dependence of the degree of alignment. The obtained values are compared with recent theoretical calculations and are found to agree well within the experimental uncertainties.     

Field-induced alignment of oxygen and nitrogen by intense femtosecond laser pulses

Field-induced alignment of O2 and N2 was experimentally studied with laser intensities varying from 10(13) to 10(15) W/cm2. When the laser intensity was below the ionization threshold for these molecules, the interaction between the induced dipole moment of molecules and the laser electric field aligned the molecules along the laser polarization direction. After extinction of the exciting laser, the transient alignment revived periodically. Thus macroscopic ensembles of highly aligned O2 and N2 molecules were obtained under field-free conditions. When the laser intensity exceeded the ionization threshold for these molecules, multielectron ionization and Coulomb explosion occurred. Using two linearly polarized laser pulses with crossed polarization, we demonstrated that the rising edge of the laser pulse aligned the molecules along the laser polarization direction prior to ionization, which resulted in strong anisotropic angular distributions of exploding fragments. These results suggest that the degree of alignment should be taken into account when qualitatively comparing the ion yield of these molecules with their companion atoms.     

Electrical field effects on dipole moment, structure and energetic of (H2O)n (2 n 15) cluster

The effect of an external electric field on water clusters of the (H₂O)_n type, with [1 n 15], in the ground state was analyzed at the B3LYP/cc-pVTZ level of theory. The calculations showed that an external electric field changes the number of hydrogen bonds, reduces the cluster sizes and increases the strength of the inter-cluster hydrogen bonds. The particular symmetry of the cluster and the null dipole moment in these specific configurations suggest that their stability can be associated with a perfect alignment of the water molecules, maximizing attractive electrostatic interactions caused by changes in the charge distribution of the clusters.     

Electron scattering with H2S and PH3 molecules

Calculated total, differential and momentum transfer cross sections are reported for the vibrationally elastic scattering of electrons from H₂S and PH₃ molecules in the range of energy 0.1–50 eV. The scattering process is approximated by two incoherent scatterings caused, separately, by a central field and a long-range electric dipole interaction. The central field is calculated with a spherical approximate molecular wave function, in which the exchange interaction is treated in two ways: (i) exactly within the accuracy of the molecular wave function; (ii) approximately by a local model potential. The scattering by the central field is calculated with partial wave expansion technique, while the scattering by the electric dipole potential is calculated by using the first Born approximation for a rotating dipole model with experimental values of the dipole moments of H₂S and PH₃. The total cross sections are approximated by the incoherent sum of the cross section due to the central potential and the cross section of 00→10 rotational transition caused by the electric dipole potential. The effects of the polarization interaction are also tested. The contribution of small-angle scattering to the integral cross section is analyzed for these weakly polar molecules with some quantitative comparison.     

Laser control of potential energy surface crossing in ion-molecule reactions application to Na+ + CH4

Laser ion-molecule reaction interaction through dipole moments leads to potential energy sur-face crossings. We will show here by using gauge representation (electric field gauge) that we can induce laser promoted surface crossing in the region (2 a.u.) where the dipole moment changes sign. We illustrate such effects for the NaH + CH₃⁺ ↔ Na⁺ + CH₄ reaction which takes the form of inverted Morse potential (without a barrier) using ab initio methods for calculating the reaction path and the permanent dipole moment of this ion-molecule reaction.     

Matrix-induced Linear Stark Effect of Single Dibenzoterrylene Molecules in 2,3-Dibromonaphthalene Crystal

Absorption and fluorescence from single molecules can be tuned by applying an external electric field – a phenomenon known as the Stark effect. A linear Stark effect is associated to a lack of centrosymmetry of the guest in the host matrix. Centrosymmetric guests can display a linear Stark effect in disordered matrices, but the response of individual guest molecules is often relatively weak and non-uniform, with a broad distribution of the Stark coefficients. Here we introduce a novel single-molecule host-guest system, dibenzoterrylene (DBT) in 2,3-dibromonaphthalene (DBN) crystal. Fluorescent DBT molecules show excellent spectral stability with a large linear Stark effect, of the order of 1.5 GHz/kVcm⁻¹, corresponding to an electric dipole moment change of around 2 D. Remarkably, when the electric field is aligned with the a crystal axis, nearly all DBT molecules show either positive or negative Stark shifts with similar absolute values. These results are consistent with quantum chemistry calculations. Those indicate that DBT substitutes three DBN molecules along the a-axis, giving rise to eight equivalent embedding sites, related by the three glide planes of the orthorhombic crystal. The static dipole moment of DBT molecules is created by host-induced breaking of the inversion symmetry. This new host–guest system is promising for applications that require a high sensitivity of fluorescent emitters to electric fields, for example to probe weak electric fields.     

Simulation studies of dipole correlation in the isotropic liquid phase

The Kirkwood correlation factor g₁ determines the preference for local parallel or antiparallel dipole association in the isotropic phase. Calamitic mesogens with longitudinal dipole moments and Kirkwood factors greater than 1 have an enhanced effective dipole moment along the molecular long axis. This leads to higher values of Δ? in the nematic phase. This paper describes state-of-the-art molecular dynamics simulations of two calamitic mesogens 4-(trans-4-n-pentylcyclohexyl)benzonitrile (PCH5) and 4-(trans-4-n-pentylcyclohexyl)chlorobenzene (PCH5-Cl) in the isotropic liquid phase using an all-atom force field and taking long range electrostatics into account using an Ewald summation. Using this methodology, PCH5 is seen to prefer antiparallel dipole alignment with a negative g₁ and PCH5-Cl is seen to prefer parallel dipole alignment with a positive g₁; this is in accordance with experimental dielectric measurements. Analysis of the molecular dynamics trajectories allows an assessment of why these molecules behave differently.     

A new form of spontaneously polarized material

We report here the discovery of a new form of spontaneously polarized material. Examples of this material, in the form of films, demonstrate the property that they spontaneously harbour electric fields which may exceed 10(8) Vm(-1), achieving potentials of tens of volts on the film surface. The molecules presently identified form a diverse group, thus far of six species, with gas phase dipoles lying between 0.08 D and 0.5 D: propane (0.08 D), isopentane (0.13 D), nitrous oxide (0.167 D), isoprene (0.25 D), toluene (0.385 D) and CF(3)Cl (Freon-13; 0.5 D). Here we concentrate on an understanding of the nature of the interactions which give rise to the spontaneously polarized state, using the measured temperature dependence of the electric field in N(2)O as a diagnostic. We show that the polarized state can arise through a mechanism of non-linear dipole alignment in a single domain in which dipole alignment generates the electric field within the film and the field generates dipole alignment. Non-local interactions take place over the dimension of the thickness of the film and permeate the entire medium through the agency of the electric field. This new type of material may have wide ranging applications in devices and in nanotechnology.     

Stark-selected beam of ground-state OCS molecules characterized by revivals of impulsive alignment

We make use of an inhomogeneous electrostatic dipole field to impart a quantum-state-dependent deflection to a pulsed beam of OCS molecules, and show that those molecules residing in the absolute ground state, X(1)Σ(+), |00(0)0>, J = 0, can be separated out by selecting the most deflected part of the molecular beam. Past the deflector, we irradiate the molecular beam by a linearly polarized pulsed nonresonant laser beam that impulsively aligns the OCS molecules. Their alignment, monitored via velocity-map imaging, is measured as a function of time, and the time dependence of the alignment is used to determine the quantum state composition of the beam. We find significant enhancements of the alignment ( = 0.84) and of state purity (>92%) for a state-selected, deflected beam compared with an undeflected beam.     

Director distribution in field-induced undulated structures of cholesteric liquid crystals

Structures with a periodic in-plane liquid crystal director field modulation induced by an electric field are studied in cholesteric liquid crystals (CLCs). A phenomenon of the electric-field-induced instability in a planarly aligned cholesteric cell is used to create these undulated structures. The initial field-off state is planarly aligned with the cholesteric helix axis oriented perpendicular to the cell substrates. The interaction of the CLC with an electric field results in modulation of the refractive index, which is visualised as stripe domains oriented either along or perpendicular to the rubbing direction at cell alignment surfaces. The threshold electric field for the undulation appearance and a period of stripes are measured experimentally for three Grandjean zones (ratio d/p ~ 0.5, 1.0, and 1.5, where d is a cell thickness and p is the natural cholesteric pitch). For the zone with d/p ~ 1.0 using numerical simulations, we describe in detail the director distribution at an applied electric field. It is found that the in-plane undulated structure is characterised by a conical director rotation on moving along the alignment direction. The conical axis is tilted with respect to the alignment axis. The sign of the tilt angle depends on the handedness of CLC.     

Nanosecond photofragment imaging of adiabatic molecular alignment

Adiabatic alignment of CH(3)I, induced by the anisotropic interaction of this symmetric top molecule with the intense field of a nonresonant infrared laser pulse, has been studied using velocity map imaging. We are using photodissociation imaging with pulsed nanosecond lasers to probe the distribution of the molecular axis in the laboratory space. In contrast to the commonly used probing with femtosecond laser pulses, this technique directly yields the degree of alignment over an extended space-time volume. This will be relevant for future reactive scattering experiments with laser-aligned molecules. The obtained degree of alignment, (cos?(2)θ), measured as a function of the infrared laser intensity, agrees well with a quantum calculation for rotationally cold methyl iodide. The strong infrared laser is also found to modify the photofragmentation dynamics and open up pathways to CH(3)I(+) formation and subsequent fragmentation.     

Mechanism of nematic molecular alignment based on friction charges and surface topology by rubbing

A new and simple electric charge interaction mechanism has been proposed to explain the behaviour of the tilt angle of liquid crystals by rubbing. The mechanism of the molecular alignment is elucidated based on the effect of a static electric charge on a substrate surface treated by rubbing. An electric field which is dependent on the topology of a substrate surface allows a planar orientation of molecules with positive dielectric anisotropy. With increasing rubbing strength, the tilt angle varies slowly. The director of molecules with negative dielectric anisotropy is uniform and has a tilt angle determined by the molecular permanent dipole direction. The air-liquid crystal interface case is also considered. This model enables us to give a unified picture of the molecular alignment mechanism.     

Light‐Driven Reversible Alignment Switching of Liquid Crystals Enabled by Azo Thiol Grafted Gold Nanoparticles

Stimuli‐directed alignment control of liquid crystals (LCs) with desired molecular orientation is currently in the limelight for the development of smart functional materials and devices. Here, photoresponsive azo thiol (AzoSH) was grafted onto gold nanoparticles (GNPs). The resulting hybrid GNPs were able to homogeneously mix with a commercially available nematic LC host, as evidenced by Cryo‐TEM. Interestingly, the LC nanocomposites were found to undergo reversible alignment transition upon light irradiation as a consequence of the trans–cis photoisomerization of the azo groups on the GNP surface. LC molecules in either planar or bare glass cells were able to change their alignment to vertical upon UV irradiation, while the vertically aligned LC molecules returned to the planar or random orientation under visible irradiation. Neither the azo thiol molecules nor the unfunctionalized GNPs alone promoted the alignment of the LC molecules in the system upon light irradiation. The photoinduced vertical alignment without applied electric or magnetic field was very stable over time and with respect to temperature. Furthermore, an optically switchable device based on the photostimulated reversible alignment control of LCs was demonstrated.     

First principle study of adsorption of boron-halogenated system on pristine graphyne

To ensure the possibility of using graphyne as a gas sensor, we have studied the adsorption of boron-halogenated system on pristine graphyne with the help of density functional theory using generalized gradient approximation. Depending on binding energy the most stable orientation, adsorption strength and optimal distance between the above mention molecules and graphyne surface have been determined. The band gap of graphyne slightly increases with the adsorption of the boron-halogenated system. The graphyne system behaves as n-type semiconductor when it interacts with BI₃ and BCl₃ molecules, and it behaves as p-type semiconductor when interaction with BF₃ molecule takes place. Our result reveals that the electronic properties of pristine graphyne are highly influenced by the adsorption of boron-halogenated molecule. We have observed that pristine graphyne has zero electric dipole moment, but with the interaction of boron-halogenated molecule, a significant change in the electric dipole moment takes place. Hence, by measuring the electric dipole moment change, graphyne-based gas sensor can be design for the detection of above-mentioned molecules.     

A bilayer model of the double hysteresis loop in antiferroelectric liquid crystals

We investigate, both analytically and numerically, a simple model of the field induced double hysteresis loop in AFLC materials. This bilayer model of the bulk of an AFLC describes the free energy in terms of polar and non-polar interactions due to surface alignment, the electric field/dipole interaction in each layer and the dipole/dipole interaction between the layers. The static hysteresis loop is found analytically and the stability of each analytic solution is investigated. The dynamic switching characteristics are found numerically and then investigated as the system parameters and electric field characteristics are changed.     

Energy transfer between Eu2+ ions in RbMgF3 crystals

Time-resolved spectroscopy after pulsed nitrogen laser excitation was used to characterize the energy transfer between Eu²⁺ ions in different crystal field sites in RbMgF₃ crystals. The results are consistent with electric dipole—dipole interaction and indicate that the Eu²⁺ ions are forming clusters in this host. As temperature is raised, the upper crystal field components of the metastable states of the ions become thermally populated and this changes the characteristics of the transfer process.     

Trapping of DNA by dielectrophoresis

Under suitable conditions, a DNA molecule in solution will develop a strong electric dipole moment. This induced dipole allows the molecule to be manipulated with field gradients, in a phenomenon known as dielectrophoresis (DEP). Pure dielectrophoretic motion of DNA requires alternate current (AC) electric fields to suppress the electrophoretic effect of the molecules net charge. In this paper, we present two methods for measuring the efficiency of DEP for trapping DNA molecules as well as a set of quantitative measurements of the effects of strand length, buffer composition, and frequency of the applied electric field. A simple configuration of electrodes in combination with a microfluidic flow chamber is shown to increase the concentration of DNA in solution by at least 60-fold. These results should prove useful in designing practical microfluidic devices employing this phenomenon either for separation or concentration of DNA.