Experimental study of de Vries properties in antiferroelectric smectic liquid crystals

Results of the experimental study on different antiferroelectric liquid crystal (AFLC) materials are presented using a number of techniques such as the optical birefringence, electro-optics and the measurements of optical thickness of free-standing films. Despite differences in the molecular structures of the various AFLC materials studied, these are found to exhibit a de Vries type of smecticA^* (SmA ^*) properties in a temperature range higher than SmC ^* . This correlation leads to the conclusion that these two classes of liquid crystals are related to each other. Furthermore, we suggest that these arise from the same physical mechanism, namely the existence of the weak synclinic (or reduced anticlinic) correlations between the neighbouring molecular tilt directions.     

Study of the molecular tilt angle and the order parameter of a ferroelectric liquid crystal mixture using IR spectroscopy

We report measurements of the molecular tilt angle of a ferroelectric liquid crystal mixture (ZLI 3654), using infra-red spectroscopy, and of the optical tilt angle using polarizing microscopy. The molecular tilt angle is found to be approximately the same for different molecular vibrations. The second rank orientational order parameter for the axis of molecular vibrations of different groups of the molecule for homogeneously aligned samples have been determined as a function of temperature. The order parameter depends slightly on the sample thickness and is about 8 per cent higher for a lower thickness (∼ 7 μm) compared to a higher thickness (∼ 12 μm). The order parameter does not change significantly at the S_C*-S_A transition. The order parameter of S_C* is found to be unaffected by the application of a constant electric field. The order parameter for the alkyl chain is found to be about three times lower than for the molecular core.     

Triphenylmethyldifluoramine: a stable reagent for the synthesis of gem-bis(difluoramines)

The conversion of ketones into geminal bis(difluoramines) can be achieved under mild two-phase reaction conditions by employing triphenylmethyldifluoramine as an in situ source of difluoramine.     

Submillimetre laser spectroscopy of intensely absorbing liquids

The submillimetre spectra of several intensely absorbing liquids have been measured with a tunable submillimetre laser at several spot frequencies in the range from about 20 to 200cm^?1. The spot frequency measurements enable us to check the accuracy of broadband power absorption spectra obtained by Michelson interferometry under a range of conditions and for several different types of heavily absorbing liquids, including aqueous solutions of current interest.     

Conformational distribution of a ferroelectric liquid crystal revealed using fingerprint vibrational spectroscopy and the density functional theory

The authors have investigated the conformational structure of the ferroelectric liquid crystal compound 4-3-methyl-2-chloropentanoyloxy-4"-hexyloxy-biphenyl also known under the abbreviations 3M2CPHOB and C6 using vibrational (IR and Raman) spectroscopy. The measured spectra exhibit two bands corresponding to the C=O stretching vibration that are separated by 20 cm(-1). In contrast, the molecular structure comprises only one such group. They assigned the two bands to different conformers that coexist in a temperature range between 25 and 65 degrees C covering the entire mesophase of this material. This assignment is strongly confirmed by calculated vibrational spectra based on the density functional theory.     

Relaxations and nano-phase-separation in ultraviscous heptanol-alkyl halide mixture

To gain insight into the effects of liquid-liquid phase separation on molecular relaxation behavior we have studied an apparently homogeneous mixture of 5-methyl-2-hexanol and isoamylbromide by dielectric spectroscopy over a broad temperature range. It shows two relaxation regions, widely separated in frequency and temperature, with the low-frequency relaxation due to the alcohol and the high-frequency relaxation due to the halide. In the mixture, the equilibrium dielectric permittivity epsilon(s) of the alcohol is 41% of the pure state at 155.7 K and epsilon(s) of isoamylbromide is approximately 86% of the pure state at 128.7 K. The difference decreases for the alcohol component with decreasing temperature and increases for the isoamylbromide component. The relaxation time tau of 5-methyl-2-hexanol in the mixture at 155.7 K is over five orders of magnitude less than in the pure state, and this difference increases with decreasing temperature, but tau of isoamylbromide in the mixture is marginally higher than in the pure liquid. This shows that the mixture would have two T(g)'s corresponding to its tau of 10(3) s, with values of approximately 121 K for its 5-methyl-2-hexanol component and approximately 108 K for its isoamylbromide component. It is concluded that the mixture phase separates in submicron or nanometer-size aggregates of the alcohol in isoamylbromide, without affecting the latter's relaxation kinetics, while its own epsilon(s) and tau decrease markedly.     

In Pursuit of the PO2+ Cation. The Reaction of KPO2F2 and SbF5 leads to an Eight‐membered Antimony‐Oxygen‐Phosphorus‐bridged Ring

The reaction of KPO₂F₂ with the strong Lewis acid SbF₅ was studied as a potential pathway to the unknown PO₂⁺ cation. The resulting product has the desired PO₂SbF₆ composition but consists of an eight‐membered, antimony‐oxygen‐phosphorus‐bridged ring that was characterized by vibrational and NMR spectroscopy, ab initio methods, and a single crystal x‐ray diffraction study. The preferred formation of the ring and its mechanism are discussed.     

Near-edge X-ray absorption fine structure spectroscopy and structural properties of Ni-doped CeO2 nanoparticles

Ni-doped CeO₂ nanoparticles were prepared by using the co-precipitation method. The prepared nanoparticles were characterized using X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, field emission scanning electron microscopy (FE-SEM) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The XRD results infer that Ni-doped CeO₂ nanoparticles have single phase nature similar to that of pure CeO₂ nanoparticles. We have calculated lattice parameters using Powder-X software, particle size using Scherer’s formula and strain using the Williamson-Hall method for all the synthesized samples. We have observed a systematic decrease in the lattice parameters, particle size and strain with an increase in Ni doping in CeO₂. The FE-SEM micrographs also confirm that Ni-doped CeO₂ have nanocrystalline behavior and particles are spherical shaped. From the Raman spectra, it is observed that the intensity of classical CeO₂ vibration modes first increases then decreases with Ni doping. The NEXAFS spectra measured at Ce M_4,5 and Ni L_3,2 edges clearly indicate that Ce ions are in the +4 valence state and Ni ions are in the +2 valence state.