Kerr effect in the critical solutions of propionitrile

The electrooptical Kerr effect (EKE) has been measured in four critical propionitrile-hydrocarbon systems covering a wide range of refractive indices as well as the density mismatch between the components. Precritical EKE anomalies are strongly solvent-dependent and they have been observed only in the mixtures with distinctly pronounced critical opalescence and different electric permittivities of the components. The solvent influences the critical amplitude, but not the critical exponent, the latter being close to 0.7 for the examined systems. The possible mechanisms of the field-induced optical anisotropy of the solutions are discussed.     

Optical Kerr effect in carbon diselenide

We have measured the optical Kerr susceptibility of liquid carbon diselenide and find its value to be (74 ± 11) × 10^?14 csu, with pump and probe wavelengths of 619 and 579 nm, respectively. This value is approximately three times the Kerr susceptibility of carbon disulfide, and is the largest value reported for a simple liquid. A strong dispersion in Kerr susceptibility is observed as the probe frequency is tuned toward the blue, and is likely due to two-photon near-resonant enhancement from the ¹B₂ state. We also report the visible and ultraviolet absorption spectra and linear refractive index measurements of liquid CSe₂.     

Kerr effect in the isotropic melt of smectic polymer

Electric birefringence in the isotropic melt of a comb-like polyacrylate with mesogenic cyanobiphenyl side groups has been studied. A fraction with the degree of polymerization 200, which forms a smectic mesophase, has been considered. The change in the character of the temperature dependence of the Kerr constant has been revealed in the isotropic phase above the smectic–isotropic phase transition temperature. This effect is explained by the change in the character of short-range order in the isotropic–isotropic phase transition.     

Measurement of the Kerr effect in cholesteric blue phases

The electric field induced birefringence within the blue phases and the isotropic phase of several different liquid crystals has been measured. The temperature dependences within the blue phases are found to be strong, characteristically different for each phase, and unlike what is predicted by simple theoretical arguments.     

Kerr effect investigations in a liquid crystal

Measurements are reported for the d.c. Kerr response and the pretransitional behaviour of a new liquid crystal, 4-cyanophenyl 4-pentylbenzoate at and above the nematic-isotropic phase transition temperature. The real parts of the third order nonlinear susceptibilities chi⁽³⁾ at and above the nematic-isotropic transition temperatures are determined for the new liquid crystal from the electro-optic Kerr effect (EOKE) experiments. The variation of the Kerr constant with temperature is discussed on the basis of the Landau-de Gennes model of the nematic-isotropic phase transition. The susceptibility values are also compared with that of the well known liquid crystal 4'-pentyl-4-cyanobiphenyl (5CB). The effect of the linking group of the liquid crystal on the suceptibility value is also discussed.     

Damping of sound waves in the terahertz range and strength of the boson peak

By applying a new two-step line-shape analysis to inelastic neutron and x-ray scattering spectra of glassy systems, we were able to resolve the acoustic excitations from the low-frequency excess modes and to accurately estimate the damping of sound waves in the terahertz frequency range. Using this approach, we estimated the damping parameter for terahertz acoustic waves in a wide class of chemically different glasses and did a quantitative comparison of the results with prediction of theoretical models. By comparing the estimates of the mean-free path of the acoustic modes in different glasses and the corresponding boson peak strengths, we show the existence of a simple correlation between these two quantities. The relationship between attenuation of the terahertz acoustic modes, strength of the boson peak, and fragility is discussed.     

Anomalous nonlinear dielectric and Kerr effect relaxation steady state responses in superimposed ac and dc electric fields

It is shown how the rotational diffusion model of polar molecules (which may be described in microscopic fashion as the diffusion limit of a discrete time random walk on the surface of the unit sphere) may be extended to anomalous nonlinear dielectric relaxation and the dynamic Kerr effect by using a fractional kinetic equation. This fractional kinetic equation (obtained via a generalization of the noninertial kinetic equation of conventional rotational diffusion to fractional kinetics to include anomalous relaxation) is solved using matrix continued fractions yielding the complex nonlinear dielectric susceptibility and the Kerr function of an assembly of rigid dipolar particles acted on by external superimposed dc E0 and ac E1(t)=E1 cos omegat electric fields of arbitrary strengths. In the weak field limit, analytic equations for nonlinear response functions are also derived.     

Some observations on the Kerr effect in suspensions of bentonite

Apparatus is described which allows continuous electro-optic signals to be obtained from aqueous suspensions of bentonite. A radiofrequency-field generator and external electrodes are used to allow the suspension to be contained in an all-glass cell. The magnitude of the response is found to depend both on cation charge and on concentration. There appears to be little chemical selectivity save under circumstances which cause the ion population available to the suspension to be depleted.     

Anomalous Kerr effect relaxation in an alternating field

Perturbation theory is used to derive the complex harmonic components (stationary regime) arising in Kerr effect relaxation for an assembly of nonelectrically interacting, polar, and polarizable symmetric-top molecules acted on by a strong dc bias electric field superimposed on a weak ac electric field. The approach starts from a fractional kinetic equation written in configuration space and represents an extension of the Smoluchowski equation to fractional dynamics. This equation is solved in the context of a subdiffusive process characterized by an anomalous exponent alpha ranging from 0 to 1, the Brownian limit. By using a perturbation procedure restricted to the second order in the ac field strength, analytic expressions for the electric birefringence spectra representing the frequency dependence of the first (in omega) and the second (in 2omega) harmonic components are obtained. Various Cole-Cole-like diagrams are presented in order to illustrate the results so obtained and to emphasize the role played by the fractal parameter alpha in the anomalous diffusion collision process. A comparison of our theoretical model with experimental measurements of the ac Kerr effect response of a dilute polymer solution [poly(3-hexylthiophene)] appears to be quite satisfactory.     

Kerr effect in ternary W/O microemulsions

A recent model accounting for the negative electric birefringence contribution observed in some microemulsion systems is compared with available measurements. The microemulsion system has been studied by complementary techniques, so that the main parameters of the model are known independently. After some adjustments, good agreement between theory and experiments has been obtained.     

Temperature dependence of the Kerr effect of hydrogen sulphide

The Kerr effect fo gaseous hydrogen sulphide was measured from 254–341 K and (1.5–16.7) ×10⁵ Pa. The difference between the polarizability in the direction of the molecular dipole and the mean is (?0.029 ± 0.008) × 10^?40 C² m² J^?1. With literature data, this yields all three principal polarizabilities. The first hyperpolarizability β^K is obtained.     

The birefringence and extinction coefficient of positive and negative liquid crystals in the terahertz range

Birefringence and extinction coefficients of positive nematic liquid crystal (NLC) MLC-2142 and negative NLC BHR28000-400 are measured by terahertz time-domain spectroscopy system (THz-TDS). Frequency ranging from 0.1 to 0.6 THz, the birefringence of positive NLC MLC-2142 increases with the increase of frequency, and keeps larger than 0.23, which exhibits application potential in tunable broadband LC THz device where a large birefringence is required. In contrast, the birefringence of BHR28000-400 decreases with the increased frequency, which shows a completely different optical property from the positive NLC. The extinction coefficient of the above two kinds of liquid crystals are also investigated.     

Relaxation of the optical Kerr effect of anisotropic molecules in mixed liquids

The relaxation time of the Kerr effect of nitrobenzene and m-nitrotoluene in various mixtures with carbon tetrachloride and various alcohols was determined by measuring the kinetics of the Kerr effect using picosecond laser techniques. These measurements yield information on the rotational motion of molecules in liquids. The relaxation time data are interpreted in terms of an effective local viscosity effect, pair correlation, and coupling of rotational motion with shear modes.     

Synthesis and Kerr effect of p-phenylene vinylene oligomers

The molecular dynamics of p-phenylene vinylene (PPV) oligomers, synthesised by a condensation reaction and separated by molecular distillation, have been investigated using the electrooptic Kerr effect. The experimental Kerr constants of these materials change sign from positive to negative in going from n = 1 to n = 2 and are not in good agreement with theoretical results. The discrepancies, which increase in magnitude as n increases, can be attributed to solvent-solute interactions, the nonplanar nature of PPV oligomers, or the nonvalidity of the additivity scheme chosen for calculation of theoretical quantities. © 1996 John Wiley & Sons, Inc.     

Temperature-dependent optical Kerr effect spectroscopy of aromatic liquids

Ultrafast optical Kerr effect (OKE) spectroscopy has been used to study the temperature-dependent dynamics of five aromatic liquids: benzene, benzene-d(6), hexafluorobenzene, mesitylene, and 1,3,5-trifluorobenzene. The intermediate response time of all of the liquids was found to scale with the collective orientational correlation time, as has been observed for other simple liquids. The spectra of hexafluorobenzene, 1,3,5-trifluorobenzene, and mesitylene are qualitatively different from those of the other liquids and exhibit different behavior with temperature. These spectra allow us to assess the influence of different molecular parameters on the shape of the OKE spectrum. On the basis of these data, we propose a model that links the differences in the OKE spectra to corresponding differences in the local ordering of the liquids.     

Searching for voids in liquids with optical Kerr effect spectroscopy

It has recently been shown [J. Chem. Phys. 2005, 122, 134506; J. Am. Chem. Soc. 2006, 128, 5119] that liquid tetrahydrofuran has an unusual structure that features voids of significant dimension. Such voids should affect other observable properties of this liquid. Here we present temperature-dependent, optical Kerr effect data for tetrahydrofuran and a number of related liquids (furan, cyclopentane, tetrahydropyran, cyclohexane, diethyl ether, and n-pentane) as well as hexamethylphosphoramide to test whether this technique can be used to reveal the presence of sizable voids in liquids.     

Application of the electro-optic Kerr effect to investigation of the intermolecular H-bond

The intermolecular H-bond plays an important role in chemical and biological systems and processes. This review considers various aspects of the application of the electro-optic Kerr effect in the investigation of the intermolecular H-bond. Current approaches to the determination of structures of H-bonded molecular complexes are described. From the measurements of the electro-optic and molar Kerr constants of the complexes and their individual components these methods produce the basic parameters of the H-bonded complexes, including the complex formation equilibrium constant (K) and the H-bond dipole moment (μ_H). The importance of a new parameter, namely, the structural additive difference of the molar Kerr constants (ΔmK)_S is illustrated. The prospects of future progress in the studies of the intermolecular H-bond by the electro-optic methods are discussed.     

Dynamic evolution of light-induced orientation of dye-doped liquid crystals in liquid phase studied by time-resolved optically heterodyned optical Kerr effect technique

Transient evolution of light-induced molecular reorientation both in 1-amino-anthraquinone (1AAQ) dye and azobenzene doped isotropic liquid crystals (LCs) were studied by time-resolved optically heterodyned optical Kerr effect method. The results give clear direct experimental proof that under short pulse (30 ps) excitation, LC molecules orientate toward the excitation light polarization direction in the 1AAQ/LC system. However, LC molecular orientation becomes orthogonal to the light polarization in azobenzene/LC system. Time-resolved excited-state absorption of 1AAQ and wavelength dependent excited-state absorption of azobenzene were also observed and their contributions to the early dynamics of the third order optical responses of the two systems were confirmed. A simplified two-level mean-field theory was derived to reveal the intensity dependence of orientation enhancement factor in azobenzene/LC system considering the photoisomerization process.     

A new ultrafast technique for measuring the terahertz dynamics of chiral molecules: the theory of optical heterodyne-detected Raman-induced Kerr optical activity

Optical heterodyne-detected Raman-induced Kerr optical activity (OHD-RIKOA) is a nonresonant ultrafast chiroptical technique for measuring the terahertz-frequency Raman spectrum of chirally active modes in liquids, solutions, and glasses of chiral molecules. OHD-RIKOA has the potential to provide much more information on the structure of molecules and the symmetries of librational and vibrational modes than the well-known nonchirally sensitive technique optical heterodyne-detected Raman-induced Kerr-effect spectroscopy (OHD-RIKES). The theory of OHD-RIKOA is presented and possible practical ways of performing the experiments are analyzed.