INFLUENCE OF ELECTRIC FIELDS ON FLUORESCENCE QUENCHING OF CHLOROPHYLL a IN NEMATIC LIQUID CRYSTAL MATRIX

Abstract— An electric field enhances the yield of fluorescence of chlorophyll in a liquid crystal solvent. The presented data suggest that the electric field effect is caused by the decrease in the efficiency of fluorescence quenching by ions. Quenching of each polarized component of fluorescence of chlorophyll molecules oriented by the liquid crystal matrix is different. The relative increase in fluorescence yield due to the applied electric field is stronger for a fluorescence component polarized parallel to the direction of liquid crystal orientation than for the perpendicular component.     

Electrochromism and Solvatochromism

The position and the intensity of electronic bands are influenced by an electric field. Pronounced changes in the position of absorption bands are mainly due to the dipole moment of the molecule in the ground state and the change in the dipole moment during the excitation process, and pronounced changes in intensity are due to the field dependence of the transition moment, which can be described by the transition polarizability. The effect of an external electric field on the optical absorption (electrochromism) of suitable molecules can be used to determine the dipole moment in the ground state, the change in dipole moment during the excitation process, the direction of the transition moment of the electronic band, and certain components of the transition polarizability tensor. These data largely determine the strong solvatochromism (solvent-dependence of the position and intensity of electronic bands), which is observed in particular with molecules having large dipole moments. Smaller contributions to solvatochromism result from dispersion interactions, which predominate in the case of nonpolar molecules. The models developed have been experimentally checked and verified by a combination of electro-optical absorption measurements (influence of an external electric field on absorption) and investigation of the solvent-dependence of the electronic bands.     

The influence of electric field-induced orientation on the retraction of a liquid crystal droplet immersed in a flexible polymer matrix

We measured the apparent interfacial tension between a liquid crystal and a flexible polymer by deformed droplet retraction method. An external electric field is applied to change the director orientation in liquid crystal droplet. The deformation and recovery of a single liquid crystal droplet dispersed in a polydimethylsiloxane (PDMS) matrix were realized by a transient shear flow and observed by polarized optical microscope. In order to control the director orientation in LC droplet, the electric field is applied perpendicular and parallel to the flow field, respectively. The different orientation induced by electric field in liquid crystal droplet has different behavior during droplet retraction and affect the apparent interfacial tension between liquid crystal and flexible polymer.     

Permeability control in electro‐sensitive microcapsules with immobilized ferroelectric liquid crystalline segments

Nylon‐polystyrene microcapsules with immobilized ferroelectric liquid crystalline segments were prepared, and permeability control of an encapsulated core material was investigated under an external electric field. A ferroelectric liquid crystal monomer possessing both mesogenicity and chirality responded effectively to the external electrical field. Permeation of the material (oxprenolol) contained in the inner aqueous core of the microcapsules was enhanced under a weak electric field (2 V). Furthermore, the permeability of oxprenolol did not depend on the external electric field in the absence of the ferroelectric liquid crystal segments. To clarify the controlled‐release mechanism of the core material, the light transmittance of the polymer membranes was quantitatively evaluated under an external electric field using a handmade polarized light transmittance apparatus. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1749–1757, 2008     

External electric field effects on absorption, fluorescence, and phosphorescence spectra of diphenylpolyynes in a polymer film

External electric field effects on absorption, fluorescence, and phosphorescence spectra of a series of unsubstituted diphenylpolyynes have been examined in a PMMA film. The analysis of the electroabsorption spectra indicates that the shorter diphenylpolyynes exhibit only the change in molecular polarizability, whereas the longer ones exhibit the change both in dipole moment and in molecular polarizability following absorption. The finding of the change in dipole moment following absorption of centrosymmetric diphenylpolyynes is interpreted in terms of the symmetry distortion upon doping a polymer film. When the external electric field is applied, the fluorescence yield is reduced and enhanced, respectively, in diphenylacetylene and diphenyloctatetrayne, indicating that the rate of the nonradiative process from the fluorescence state is accelerated in diphenylacetylene and decelerated in diphenyloctatetrayne by an external electric field. All of the diphenylpolyynes used in the present study exhibit the change in molecular polarizability following the phosphorescence process.     

Opto-thermal reorientation of nematics with two-fold degenerate alignment

The preferred direction of alignment of the liquid crystal molecules in nematics with two-fold degenerate alignment can be affected substantially by changing the temperature or by applying an electric field. As a result, an almost in-plane switching of the molecules occurs. Here, we report an opto-thermal reorientation effect in a nematic with two-fold degenerate alignment due to a local heating of the liquid crystal by a high power laser beam. The mechanism of this phenomenon is discussed. The opto-thermal reorientation of the molecules makes it possible to visualize the temperature distribution in the illuminated cell and some applications can be foreseen.     

Tunable polarised fluorescence of quantum dot doped nematic liquid crystals

The concentration, excitation photon wavelength, and polarisation dependent fluorescence of quantum dot (QD)–liquid crystal (LC) mixtures has been studied at room temperature using high-resolution, steady-state fluorescence spectroscopy. The fluorescence of QD–LC mixture increases with increasing QD’s concentration but the spectral red shift of ~10 nm relative to the stock QD–Toluene solution remains independent of concentration. In vertical switching (VS) cells, an external electric field changes the LC alignment direction and enhances the apparent fluorescence intensity. The apparent fluorescence anisotropy compared to that at zero applied electric field monotonically increases up to ~27% at an applied electric field of 0.6 V/µm. These results are consistent with the formation of disc-like assemblages of QDs oriented on planes perpendicular to the director of the nematic liquid crystal (NLC). These findings have important utility in polarisation sensitive photonic devices.     

Polarized infrared study of a polymer network deformation in a nematic liquid crystal host

Using polarized infrared (IR) spectroscopy we have observed deformation of a polymer network in a liquid crystal host during the reorientation of the liquid crystal by an external electric field. In the system studied, containing 2% BMBB-6 polymerized at zero applied field in the host nematic liquid crystal 6CB, the observed deformation angle was between 20^o and 40^o +/- 10^o. These experimental results provide some of the first conclusive experimental evidence that the polymer network elastically deforms as a direct result of the reorientation of the liquid crystal host.     

The electro-optical properties of 'charged' PDLCs

The application of high intensity electric fields to polymer dispersed liquid crystal (PDLC) films can induce changes in their electro-optical properties and morphology. In particular, a quasilinear electro-optical response to an external electric field can be achieved if an internal built-in d.c. field is induced. In this work, we show how the liquid crystal/polymer weight ratio influences the electro-optical response of 'charged' PDLCs, i.e. of PDLC films after the application of a high intensity electric field. We observed that a quasilinear electro-optical response can be achieved in a well determined range of composition. Larger liquid crystal concentrations are unable to maintain the built-in field, while PDLCs with lower liquid crystal loadings do not allow the onset of a built-in d.c. field.     

电场对聚肽液晶相行为的影响

聚合物液晶的相转变不仅可以通过溶液温度或聚合物的浓度的改变来实现,也可以通过施加外电场、磁场等取向场来达到．在二氧六环、氯仿、间甲酚等支持聚肽a一螺旋构象的溶剂中,当PBLG(聚L-谷氨酸γ-苯甲酯)达到一定的浓度会形成胆甾型溶致液晶．对这种液晶施加强度足够     

Reorientation behaviour of bent core molecules in response to an external electric field as detected by time-resolved FTIR spectroscopy

Time-resolved polarized Fourier transform infrared spectroscopy (FTIR) is employed to analyse the segmental orientation and mobility of achiral bent core molecules in response to an external electric field. By shearing the substance between ITO coated CaF2 windows two types of domain, racemic and homochiral, are formed in the high temperature B2 phase. Each of these domains is characterized by two spontaneous symmetry-breaking instabilities which yield a symmetric and an antisymmetric electro-optical response, respectively. Taking advantage of the specificity of IR spectroscopy, this switching behaviour is analysed on a molecular level for the moieties of the bent core liquid crystal materials. In this way, the electrically induced reorientation of the different segments on a cone and the suppression of the antiferroelectric structure at higher frequencies can be followed in detail. Furthermore the biased rotation of the two carbonyl groups around the molecular long axis is determined. It is shown that all molecular units move synchronously on the time scale of the experiment (10mus).     

Reorientation behaviour of bent core molecules in response to an external electric field as detected by time-resolved FTIR spectroscopy

Time-resolved polarized Fourier transform infrared spectroscopy (FTIR) is employed to analyse the segmental orientation and mobility of achiral bent core molecules in response to an external electric field. By shearing the substance between ITO coated CaF2 windows two types of domain, racemic and homochiral, are formed in the high temperature B2 phase. Each of these domains is characterized by two spontaneous symmetry-breaking instabilities which yield a symmetric and an antisymmetric electro-optical response, respectively. Taking advantage of the specificity of IR spectroscopy, this switching behaviour is analysed on a molecular level for the moieties of the bent core liquid crystal materials. In this way, the electrically induced reorientation of the different segments on a cone and the suppression of the antiferroelectric structure at higher frequencies can be followed in detail. Furthermore the biased rotation of the two carbonyl groups around the molecular long axis is determined. It is shown that all molecular units move synchronously on the time scale of the experiment (10mus).     

The electro‐optical properties of ‘charged’ PDLCs

The application of high intensity electric fields to polymer dispersed liquid crystal (PDLC) films can induce changes in their electro‐optical properties and morphology. In particular, a quasilinear electro‐optical response to an external electric field can be achieved if an internal built‐in d.c. field is induced. In this work, we show how the liquid crystal/polymer weight ratio influences the electro‐optical response of ‘charged’ PDLCs, i.e. of PDLC films after the application of a high intensity electric field. We observed that a quasilinear electro‐optical response can be achieved in a well determined range of composition. Larger liquid crystal concentrations are unable to maintain the built‐in field, while PDLCs with lower liquid crystal loadings do not allow the onset of a built‐in d.c. field.     

Polarized infrared study of a polymer network deformation in a nematic liquid crystal host

Using polarized infrared (IR) spectroscopy we have observed deformation of a polymer network in a liquid crystal host during the reorientation of the liquid crystal by an external electric field. In the system studied, containing 2% BMBB-6 polymerized at zero applied field in the host nematic liquid crystal 6CB, the observed deformation angle was between 20^o and 40^o 10^o. These experimental results provide some of the first conclusive experimental evidence that the polymer network elastically deforms as a direct result of the reorientation of the liquid crystal host.     

The effect of voltage controlled orientation order of liquid crystals in non-acrylic polymer dispersed liquid crystals films

The nematic liquid crystals (LCs) are randomly dispersed material with random orientation order in polymer dispersed liquid crystal (PDLC) films. The LCs change their orientation from random to vertical as electric field is applied. This transformation of orientation order of nematic liquid crystals in the PDLC films is controlled by many factors operating simultaneously. For instance, some factors like the internal forces of attractions among the neighboring LC molecules, anchoring with polymeric matrix, ITO glass boundaries, and chemical structures of the materials are less studied. The learning of extent of vertical orientation of liquid crystal droplets in an electric field is essential to attain optimum electro optical properties of PDLCs. In this finding, bipolar and radial LCs droplets with random orientation have been observed in non-acrylic polymeric media. It is learned that with small increase of contents of external material, the extent of vertical orientation has been varied intensely. The extent of vertical orientation of LCs molecules increases as the contents of external non-acrylic polymeric material decreased. For this study, the orientations of LCs with respect to material type/contents, external applied force, and restoration of electric filed as hysteresis have been studied in details.     

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.     

光波导分光光谱技术研究染料分子在玻璃表面的吸附特性

光波导分光光谱技术利用光波导表面的消逝场敏感地测定有色物质亚单分子吸附层的偏振吸收光谱, 非常适合于研究染料、颜料、荧光分子、量子点、金属纳米粒子、带色基的蛋白质等在固/液界面的吸附行为. 本文使用宽频带卤钨灯、棱镜耦合的薄膜玻璃光波导和基于电荷耦合器件(CCD)的光谱分析仪设计制作了具有时间分辨本领的光波导分光光谱装置, 并利用该装置实时监测了罗丹明6G(R6G)和亚甲基蓝(MB)在玻璃表面的吸附特性. 通过比较在横电(TE)和横磁(TM)偏振模式下的吸收光谱, 发现R6G主要以二聚体和单体的形式吸附在玻璃表面, 而MB主要以多聚体的形式吸附在玻璃表面, 并分别估算了它们的平均取向角.     

Proposal of a new method to determine tilt angles of absorption transition moments in host-guest liquid crystal cells

An idea for a method of experimental determination of tilt angles and order parameters of cylindrosymmetric transition moments of liquid crystals and of dyes in host-guest systems is described. Furthermore, first experimental hints are given. With freely rotating molecules, all transition moments result in an isotropic absorbance for UV/VIS-spectroscopy using polarized light. The resulting absorbance becomes anisotropic if the transition moment of the molecules is polarized, the molecules are aligned in a preferential direction, and the free rotation is suppressed. In this case, the measurement of Aiso, Atilt, and Atilt using polarized light is sufficient to calculate the related tilt angle Psi, the order parameter S, and the absorbance A as a function of the polarization angle. The local electric field and its influence on the dichroic ratio of an absorption band has not been considered. The precision of this method is still limited by the photometric accuracy of the spectrometer and the mechanical precision of the goniometric adjustment of the experimental apparatus.     

Quantitative investigation of local electric field through absorption spectrum in dye‐sensitized solar cells: Atomistic simulations

The local transient electric field in dye‐sensitized solar cells (DSSCs), created by heterointerfacial charge transfer on illumination, exerts an important role in the internal photoelectronic processes occurring at dye/semiconductor heterointerface in the time‐resolved measurement, for example, transient absorption spectroscopy. Herein, on the basis of theoretical simulations, we proposed a general strategy to quantitatively examine the nature of local electric field (microscopic nature) through absorption spectra of adsorbed dye molecule (macroscopic observation). A controllably modulated external electric field is imposed on the sensitized system to couple to local electric field, resulting in the absorption spectrum shift of ground‐state dye molecules. By fitting absorption spectrum under applied external electric field with Gauss–Stark equation, the quantitative property of local electric field would be obtained. The Gauss–Stark equation reflects the quantitative relationship between the local electric field and absorption spectrum shift of adsorbed ground‐state dye molecule. Our study not only provides origin and magnitude of Stark effect in DSSCs but also offers a promising route to explore the elementary photoelectronic processes experimentally and theoretically.     

Pulsed voltage studies of electric field effects on the optical permittivity of a nematic liquid crystal

Prism coupling to resonant optical modes in a thin layer of homeotropically aligned nematic liquid crystal has been used to characterize the change in refractive indices which occurs when an electric field is applied. Reflectivity data, recorded over a range of angles of incidence for both TE and TM radiation show sharp minima corresponding to the excitation of optical modes in the liquid crystal layer. Application of a pulsed AC voltage, pulsed to avoid heating, while synchronously monitoring reflectivity changes allows detailed characterization of the shift in the position of these minima due to the influence of the electric field on both the ordinary and extraordinary refractive indices. By fitting theoretical predictions of Fresnel theory a complete characterization of change in both these parameters up to an applied field of some 5 × 10⁶ Vm^-1 is achieved. The refractive index changes recorded are compared with the director fluctuation order parameter theory with which good agreement is found.