Fast field-cycling NMR relaxometry study of chiral and nonchiral nematic liquid crystals.

We present a proton NMR relaxometry study of the molecular dynamics in three liquid crystalline systems: 4'-n-pentyl-4-cyanobiphenyl (5CB), (S)-4'-(3-methylpentyl)-4-cyanobiphenyl (5CB*), and a 12% weight mixture of 5CB* in 5CB. The proton spin-lattice relaxation time (T1) was measured as a function of temperature and Larmor frequency in the isotropic, nematic, chiral nematic (N*), and smectic A phases of these liquid crystalline systems. A unified relaxation model was used to analyze the molecular dynamics, considering local molecular rotations/reorientations, translational self-diffusion, and collective motions as the relaxation mechanisms that contribute most effectively to the T1(-1) relaxation. Additionally, in the chiral nematic phase a fourth relaxation mechanism associated with the rotations induced by the translational diffusion along the helical axis (RMTD) was included in the model. All experimental results were consistently analyzed taking into account the physical parameters known for 5CB. The global analysis of the experimental results shows that the RMTDs are associated with the pitch value measured for the N* phases and that its contribution to the T1(-1) dispersion is observed at low frequencies. The T1(-1) dispersion in the smectic A phase of 5CB* is strongly dominated by the layer undulations relaxation mechanism over a broad frequency range from the low kilohertz regime to tens of megahertz. It was the first time such behavior was observed in a low molecular weight liquid crystalline system.

Phase structure and molecular dynamics of liquid-crystalline side-on organosiloxane tetrapodes.

X-ray diffraction and proton NMR relaxation measurements were carried out on two liquid-crystalline organosiloxane tetrapodes with side-on mesogenic groups, exhibiting nematic and smectic- C phases, and on a monomeric analog. Packing models for the mesophases exhibited by these systems are proposed on the basis of x-ray diffraction data. As a consequence of microsegregation, the aromatic cores are packed in between two sublayers formed by a mixture of interdigitated aliphatic and siloxane chains. The mixed sublayers are characteristic for the tetrapodes with side-on mesogenic groups presented in this work and have not been observed in tetrapodes with terminally attached mesogens. The tilt angle in the smectic- C phase is found very large, i.e., approximately 61 degrees -62 degrees . Notably, smectic- C clusters are present also in the whole temperature range of the nematic phase. NMR relaxometry yields T(1)-1 dispersions clearly different from those of conventional calamitics. The influence of molecular tendency to form interdigitated structures is evidenced by frequency-dependent relaxation rate in the isotropic phase-indicating the presence of ordered clusters far above the phase transition-and by the diminished role of molecular self-diffusion in ordered phases. Nematiclike director fluctuations are the dominating relaxation mechanism whereas the translational displacements are strongly hindered by the interdigitation of dendrimer arms.

Structure and molecular dynamics of the mesophases exhibited by an organosiloxane tetrapode with strong polar terminal groups.

The polymorphism of a new organosiloxane tetrapode compound with cyano terminal polar groups was characterized by means of polarizing optical microscopy and x-ray diffraction. The compound exhibits smectic- A and smectic- C phases with a partial bilayer arrangement due to a certain degree of head-to-head association of the mesogenic units through their cyano end groups. On the basis of x-ray diffraction results, evidencing the microsegregation of polyphilic molecules, packing models for the smectic- A and smectic- C phases are proposed. A high degree of smectic positional order and a relatively low value of the tilt angle in the smectic- C phase are indicated. Molecular dynamics of the studied compound was investigated by means of proton NMR relaxometry. The frequency dispersions of the spin-lattice relaxation time (T1) show that the relaxation is induced by three rotational modes of individual dendrimer arms with frequencies between 10;{6} and 10;{9}Hz . In the smectic phases, the effect of individual rotations is overwhelmed by a well expressed contribution of layer undulations at Larmor frequencies below approximately 10MHz . The appearance of this relaxation mechanism over the frequency range of three decades is so far unique in the case of thermotropic liquid crystals. The analysis of the layer undulations contribution supports the microsegregation model of the smectic phases by revealing a slowing-down of translational diffusion and the lack of interactions among the sublayers formed by the mesogenic groups.

Liquid crystal 8CB in random porous glass: NMR relaxometry study of molecular diffusion and director fluctuations.

We present the measurements of the proton spin-lattice relaxation time T1 of liquid crystal 4-n-octyl-4'-cyanobiphenyl (8CB) confined into randomly oriented approximately 15 nm pores of untreated porous glass. In the low kilohertz range the spin-lattice relaxation rate in the nanoconfined 8CB is about ten times larger than in the bulk. We show that the increase is mainly due to molecular reorientations mediated by translational displacements (RMTD). In the paranematic phase the power law describing the RMTD dispersion, (T1(-1))RMTD proportional, omega(-p), is well characterized by the exponent p=0.5+/-0.06 and suggests an equipartition of diffusion modes with different wavelengths. The largest distance related to the decay of the orientational correlation function is about twice the diameter of the cavity. The situation is different in the nematic phase, where the orientational correlation is eventually lost at approximately 60 nm in the direction along the pore, a distance corresponding roughly to the length of a pore segment in the glassy matrix. The exponent p is between 0.65 and 0.9, depending on the temperature, which implies that in the nematic phase long wavelength modes are relatively more important--a consequence of the uniform director field along the pore. These observations are in agreement with the model of mutually independent pores with nematic director parallel to the pore axis in each segment. We point out that in strongly confined liquid crystals the proton NMR relaxometry does not provide the evidence of director fluctuations correlated over micrometer distances as was suggested earlier. The local translational diffusion of molecules within the cavities is found about as fast as in bulk.

Anchoring and structural transitions as a function of molecular length in confined liquid crystals.

Using deuteron nuclear magnetic resonance to study liquid crystals confined to cylindrical pores, an anchoring transition has been found. The transition exhibits an unexpected sharp dependence of the anchoring strength on cyanobiphenyl liquid crystal molecular length. A structural transition from a parallel axial to a planar radial configuration occurs due to an anchoring transition from planar to weakly homeotropic orientation at the walls. The anchoring strength is at a minimum near the decylcyanobiphenyl (10CB) liquid crystal length. Long chain liquid crystal configurations depend on thermal cycling and on the equilibrium atmosphere leading to a bistable SmA structure. Orientational order wetting in the isotropic phase also depends on molecular length.

Field-cycling NMR relaxometry of a liquid crystal above in mesoscopic confinement.

We measured the proton spin-lattice relaxation times in the isotropic phase of liquid crystal 4-n-pentyl-4-cyanobiphenyl (5CB) confined into porous glass (CPG) with the average pore diameter approximately 72 nm. The analysis of T1(-1) frequency dispersions, spanning over four decades, shows that the main relaxation mechanism induced by the ordered surface layer are molecular reorientations mediated by translational displacements (RMTD). The RMTD contribution to T1(-1) is proportional to the inverse square root of Larmor frequency, a consequence of the equipartition of diffusion modes along the surface. Low and high frequency cutoffs of the RMTD mechanism clearly reveal that the surface alignment of liquid crystal is random planar with the size of uniformly oriented patches approximately 5 nm, depending on the treatment of the CPG matrix. According to the size of the uniformly oriented patches varies also the thickness of the ordered surface layer and its temperature behavior. The surface-induced order parameter is found to be temperature independent and determined by the local short range surface interactions.

Low-frequency proton NMR relaxometry of a polymer dispersed liquid crystal above TNI.

Using proton NMR relaxometry in the kilohertz frequency range, we study dynamics of 5CB liquid crystal molecules dispersed in the form of spherical microdroplets in a PDLC material. The focus of the study is the spin-lattice relaxation in the rotating frame, T1rho(-1), measured above the nematic-isotropic transition TNI. We show that the relaxation rate T1rho(-1)--when induced by uniform molecular translational diffusion in a spherical cavity--depends on the strength of the rotating magnetic field as T1rho(-1) proportional to omega1(-alpha) where alpha varies between 0.7 and 1, depending on the thickness of the ordered surface layer. This relaxation mechanism governs mainly the transverse spin relaxation, whereas the measurements of the frequency and temperature dependence of T1rho(-1) indicate a strong effect of slowing-down of molecular translational diffusion in contact with the polymer surface and yield the average dwell-time of molecules at the surface of the order 10(-5) s.

Nuclear-spin relaxation induced by shape fluctuations in membrane vesicles.

Nuclear-spin relaxation rates resulting from shape fluctuations of unilamellar quasispherical vesicles are calculated. We show that in the kHz range these fluctuations yield-in contrast to previous conclusions on planar membranes - a relaxation rate proportional to the inverse Larmor frequency and provide direct information on the bending rigidity of membranes.

Surface-induced order and diffusion in 5CB liquid crystal confined to porous glass.

Liquid crystals confined into small cavities are known to have a weak orientational order even above the nematic-isotropic transition temperature. The surface-induced order and molecular dynamics in this temperature range are studied with the aid of deuteron NMR spectra, spin relaxation times T(1) and T(2,) proton dipolar-correlation effect, and direct measurements of the effective diffusion coefficient for the liquid crystal 5CB confined to controlled-pore glasses. Our results show that an arrangement of molecules parallel to the wall is induced by local molecular interactions between the liquid crystal and solid, resulting in a weak and temperature independent surface order parameter, S(0) approximately 0.02 +/- 0.01. There is no indication of a significant slowing-down of molecular diffusion at the wall, neither rotational nor translational. In cavities of nanometer size, where the nematic order evolves gradually upon cooling, a broadening of the NMR linewidths due to dynamic effects should be taken into account.

Aging of surface anchoring and surface viscosity of a nematic liquid crystal on photoaligning poly-(vinyl-cinnamate).

Dynamic light scattering was used to measure the azimuthal anchoring energy coefficient W(straight phi) of nematic liquid crystal (5CB) on photoaligning poly-(vinyl-cinnamate) layer. Measurements were repeated several times within two months. The results show that W(straight phi) increases in the first few days after filling the cell with liquid crystal. Then it remains approximately constant at W(straight phi)=5 x 10(-6) J/m(2) for at least two months. Also, presence of very large effective surface viscosity is observed. This phenomenon is of transient nature and attributed to swelling and dissolving of photosensitive polymer into the liquid crystal, which gives rise to an inhomogeneity of viscoelastic properties. Numerical modeling of the fluctuation spectrum shows that an inhomogeneous surface layer can account for the observed effective surface viscosity.

Measurement of the surface-induced order in polymer dispersed liquid crystals: an approach by NMR relaxometry.

A method based on NMR relaxometry is introduced to study surface-induced order in the isotropic phase of confined liquid crystals. We show that the magnitude of the surface order parameter S0 can be obtained from an increase in the deuteron transverse relaxation rate T-12. The increase originates in the molecular diffusion between the weakly ordered surface region and disordered area in the rest of the cavity. No assumptions concerning the residence time of molecules at the surface are needed. We apply the approach to a polymer dispersed liquid crystal and find a temperature independent S0 of magnitude congruent with 0.08. This indicates that short range interactions at the interface dominate the behavior of S0, and that only a partial orientational wetting occurs.