Broadband dielectric spectroscopy of a nematic liquid crystal in benzene.
27 Oct 2008-Journal of Chemical Physics (American Institute of Physics)-Vol. 129, Iss: 16, pp 164509-164509
TL;DR: For the first time, the molecular mechanism and structure of liquid crystalline materials as a function of concentration, temperature, and frequency is explained.
Abstract: Broadband dielectric spectroscopy has been used to analyze the temperature, frequency, and concentration dependences of the molecular dynamics of a nematic liquid crystal (5CB) mixed with the nonpolar solvent benzene. Differential scanning calorimetry measurement has been also performed to confirm the phase transitions of 5CB/benzene mixtures. The phase transition temperatures (crystalline to isotropic phases) thus obtained have been described very accurately from the temperature-dependent relaxation strength, the relaxation time, and the symmetric shape parameter of the relaxation function obtained from the fitting procedure. Two relaxation processes reflecting overall rotations around the short and long molecular axes are observed in both the nematic and isotropic phases. In the crystalline phase, the former process with the longer relaxation time disappeared, and latter process with shorter relaxation time shows a discontinuity at the freezing temperature. The relaxation process with shorter relaxation time obtained in the crystalline phase is larger than that obtained in the nematic phase because of the large restrictions in the crystalline phase. For the first time, we have precisely explained the molecular mechanism and structure of liquid crystalline materials as a function of concentration, temperature, and frequency.
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TL;DR: It is proposed that the polarization conductivity results from the local re-orientation of the μ(2)-OH dipoles bonded to the metal atom from the hybrid solid, i.e. Fe or Cr, and that dc conductivity, which can be ascribed to a proton propagation via a Grotthus mechanism, is favoured when the solvent molecules form strong hydrogen bonds between each other.
Abstract: The breathing behaviour of MIL-53(Cr) and MIL-53(Fe) upon water and ethanol desorption has been investigated by combining complementary experimental techniques including ThermoGravimetry Analysis (TGA), Differential Scanning Calorimetry (DSC) and Complex Impedance Spectroscopy (CIS). It was shown that two stages of solvent departure are involved in the desorption process, as revealed by (i) a change of the weight loss gradient in the TGA curve, (ii) the existence of a second endothermic peak in the DSC signal and (iii) a sudden drop and/or profile change of the ac conductivity in CIS. All these features are observed around a typical temperature Tc, for which the framework contractions, caused by the solvent desorption, occur. Moreover, it is shown that these modifications are more pronounced when the magnitude of the breathing is higher, as illustrated by the comparison of the water/MIL-53(Cr), ethanol/MIL-53(Cr) and water/MIL-53(Fe) systems. CIS data were further analyzed in the light of DFT calculations which provided the preferential arrangements of the molecules within the pores and the resulting host/guest interactions. It could then be proposed that (i) the polarization conductivity results from the local re-orientation of the μ2-OH dipoles bonded to the metal atom from the hybrid solid, i.e. Fe or Cr, and (ii) that dc conductivity, which can be ascribed to a proton propagation via a Grotthus mechanism, is favoured when the solvent molecules form strong hydrogen bonds between each other.
40 citations
TL;DR: This review article is an effort to describe the advancements in LC and nanotechnology-assisted LC systems for developing an efficient biosensor of tunable performance and will serve as a guideline to researchers who aim to fabricate a nanotechnology -assisted LC materials-based biosensor for rapid, cost-effective, selective diagnostics of a targeted disease for health care management.
39 citations
TL;DR: It is suggested that for each nCB a unique, characteristic minimal value of ΔT, associated with the I-N-SmA triple point, exists and can be hidden in the negative pressures domain for 'shorter' nCBs, and the possibility of the extension of the 'melting curve' into thenegative pressures region as well as the appearance of the'melting inversion' at high enough pressures is indicated.
Abstract: Results of the extended Landau?de Gennes model analysis and experimental studies of the isotropic?nematic (I?N) and isotropic?smectic-A (I?SmA) phase transitions in rod-like liquid crystalline n-alkylcyanobiphenyls are presented. Experiments were carried out as a function of temperature and pressure using the static dielectric permittivity and its ?nonlinear? (strong electric field related) counterpart?the low-frequency nonlinear dielectric effect. Precise estimations of the values of the discontinuity of the isotropic?mesophase transitions (?T) for nCB from n?=?3?14 have been obtained. It is suggested that for each nCB a unique, characteristic minimal value of ?T, associated with the I?N?SmA triple point, exists. For ?shorter? nCBs it can be hidden in the negative pressures domain. The possibility of the extension of the ?melting curve? into the negative pressures region as well as the appearance of the ?melting inversion? at high enough pressures is indicated.
19 citations
TL;DR: In this paper, the authors conducted dielectric and viscoelastic relaxation measurements for polystyrene (PS)/4-pentyl-4′-cyanobiphenyl (5CB) and PS/4- pentyl- 4′-cyclanoterphenyl(5CT) mixtures in the miscible state with the weight fractions of 5CB or 5CT from 0.04 to 0.27.
Abstract: We conducted dielectric and viscoelastic relaxation measurements for polystyrene (PS)/4-pentyl-4′-cyanobiphenyl (5CB) and PS/4-pentyl-4′′-cyanoterphenyl (5CT) mixtures in the miscible state with the weight fractions of 5CB or 5CT from 0.04 to 0.27 to examine the relationship between two-component dynamics in the mixture. Dielectric relaxation measurements mainly probed the dynamics of low-mass molecule (LM), 5CB or 5CT, because of the much larger dipole moment of LMs compared to that of PS. PS/5CB mixtures exhibited bimodal dielectric relaxation, while PS/5CT showed unimodal relaxation. The observed two relaxation modes (slow and fast modes) in PS/5CB were attributed to the full rotational motion and partial rotational motion of 5CB, respectively. The latter motion is allowed in the restricted space surrounded by less mobile PS matrix. In the case of 5CT, the fast mode was suppressed due to the larger size of 5CT molecule, and only the slow mode (rotational mode) appeared. The relaxation times of slow mod...
16 citations
TL;DR: Numerical simulations using the finite-differences time-domain (FDTD) technique employing an anisotropic dielectric medium allow to understand the alignment of the liquid crystal molecules on the surface of the microdisk resonator.
Abstract: Microdisks made from GaAs with embedded InAs quantum dots are immersed in the liquid crystal 4-cyano-4’-pentylbiphenyl (5CB). The quantum dots serve as emitters feeding the optical modes of the photonic cavity. By changing temperature, the liquid crystal undergoes a phase transition from the isotropic to the nematic state, which can be used as an effective tuning mechanism of the photonic modes of the cavity. In the nematic state, the uniaxial electrical anisotropy of the liquid crystal molecules can be exploited for orienting the material in an electric field, thus externally controlling the birefringence of the material. Using this effect, an electric field induced tuning of the modes is achieved. Numerical simulations using the finite-differences time-domain (FDTD) technique employing an anisotropic dielectric medium allow to understand the alignment of the liquid crystal molecules on the surface of the microdisk resonator.
14 citations
References
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TL;DR: In this paper, the locus of the dielectric constant in the complex plane was defined to be a circular arc with end points on the axis of reals and center below this axis.
Abstract: The dispersion and absorption of a considerable number of liquid and dielectrics are represented by the empirical formula e*−e∞=(e0−e∞)/[1+(iωτ0)1−α]. In this equation, e* is the complex dielectric constant, e0 and e∞ are the ``static'' and ``infinite frequency'' dielectric constants, ω=2π times the frequency, and τ0 is a generalized relaxation time. The parameter α can assume values between 0 and 1, the former value giving the result of Debye for polar dielectrics. The expression (1) requires that the locus of the dielectric constant in the complex plane be a circular arc with end points on the axis of reals and center below this axis.If a distribution of relaxation times is assumed to account for Eq. (1), it is possible to calculate the necessary distribution function by the method of Fuoss and Kirkwood. It is, however, difficult to understand the physical significance of this formal result.If a dielectric satisfying Eq. (1) is represented by a three‐element electrical circuit, the mechanism responsible...
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TL;DR: In this paper, an extension of the Onsager theory of dielectric polarization is presented, which is applied to liquid water under the assumption of tetrahedral coordination and directed bonds between neighboring molecules.
Abstract: An extension of the Onsager theory of dielectric polarization is presented. The local dielectric constant is approximated by the macroscopic dielectric constant of the fluid in a region outside a molecule and its first shell of neighbors rather than in the entire region exterior to the molecule. In addition to the molecular dipole moment, the average value 〈cosγ〉Av of the cosine of the angle between neighbor dipoles is a determining factor. Hindered relative rotation of neighboring molecules produces a correlation between their orientations and prevents 〈cosγ〉Av from vanishing. The theory is applied to liquid water under the assumption of tetrahedral coordination and directed bonds between neighboring molecules.
1,660 citations
TL;DR: In this article, the physical properties of nematic, cholesteric, and smectic liquid crystals are discussed and a wide variety of phenomena in liquid crystals, including elastic distortions, disclinations, flow properties, fluctuations, light scattering, wave propagation, nuclear magnetic resonance, effects of magnetic and electric fields, electrohydrodynamics, and optical properties.
Abstract: This review discusses the physical properties of nematic, cholesteric, and smectic liquid crystals. Molecular theories of the liquid crystal phases are discussed and the molecular field theories of the phase transitions between the various liquid crystal phases are presented. The elastic theory and hydrodynamics of liquid crystals is developed. A wide variety of phenomena in liquid crystals, including elastic distortions, disclinations, flow properties, fluctuations, light scattering, wave propagation, nuclear magnetic resonance, effects of magnetic and electric fields, electrohydrodynamics, and optical properties, is discussed.
978 citations