Molecular dynamics in liquid crystals by dielectric relaxation and neutron scattering

Abstract

Detailed dielectric permittivity and relaxation investigations have been performed on compounds having different liquid-crystalline phases. At the smectic B–smectic A as well as the smectic G–smectic B transitions definite jumps were found in the dielectric relaxation times associated with rotation of the molecules around their short axis. For the interpretation of the large jumps in the relaxation times the change of the phonon spectra at the two dimensional crystal-two dimensional liquid phase transition was assumed. To verify this idea an inelastic neutron scattering study was performed. The measurements have proved the good orientation of the smectic A and smectic B phases. The values of the layer spacing, and the appearance of libron peaks for the smectic B phase at different momentum transfer were determined.     

Structure and dynamics of halogenoethanol-water mixtures studied by large-angle X-ray scattering, small-angle neutron scattering, and NMR relaxation

To clarify the structure of solvent clusters formed in halogenoethanol-water mixtures at the molecular level, large-angle X-ray scattering (LAXS) measurements have been made at 298 K on 2,2,2-trifluoroethanol (TFE), 2,2,2-trichloroethanol (TCE), and their aqueous mixtures in the TFE and TCE mole fraction ranges of 0.002 < or = x(TFE) < or = 0.9 and 0.5 < or = x(TCE) < or = 0.9, respectively. The radial distribution functions (RDFs) for TFE-water mixtures have shown that the structural transition from inherent TFE structure to the tetrahedral-like structure of water takes place at x(TFE) approximately 0.2. In the TCE-water mixtures inherent TCE structure remains in the range of 0.5 < or = x(TCE) < or = 1. Small-angle neutron scattering (SANS) experiments have been performed on CF(3)CH(2)OD- (TFE-d(1)-) D(2)O and CF(3)CD(2)OH- (TFE-d(2)-) H(2)O mixtures in the TFE mole fraction range of 0.05 < or = x(TFE) < or = 0.8. The SANS results in terms of the Ornstein-Zernike correlation length have revealed that TFE and water molecules are most heterogeneously mixed with each other in the TFE-water mixture at x(TFE) approximately 0.15, i.e., both TFE clusters and water clusters are most enhanced in the mixture. To evaluate the dynamics of TFE and ethanol (EtOH) molecules in TFE-water and ethanol-water mixtures, respectively, (1)H NMR relaxation rates for the methylene group within alcohol molecules have been measured by using an inversion-recovery method. The alcohol concentration dependence of the relaxation rates for the TFE-water and ethanol-water mixtures has shown a break point at x(TFE) approximately 0.15 and x(EtOH) approximately 0.2, respectively, where the structural transition from alcohol clusters to the tetrahedral-like structure of water takes place. On the basis of the present results, the most likely structure models of solvent clusters predominantly formed in TFE-water and TCE-water mixtures are proposed. In addition, effects of halogenation of the hydrophobic groups on clustering of alcohol molecules are discussed from the present results, together with the previous ones for ethanol-water and 1,1,1,3,3,3-hexafluoro-2-propanol- (HFIP-) water mixtures.     

Phenylene ring dynamics in bisphenol-A-polysulfone by neutron scattering

We have investigated the dynamics of phenylene rings in a glassy polysulfone (bisphenol-A-polysulfone) by means of quasielastic neutron scattering. Nowadays it is well known that these molecular motions are directly connected with the mechanical properties of engineering thermoplastics in general. The particular system investigated by us has the advantage that by selective deuteration of the methyl groups, the neutron scattering measured is dominated by the incoherent contribution from the protons in the phenylene rings. In this way, the dynamics of such molecular groups can be experimentally isolated. Two different types of neutron spectrometers: time of flight and backscattering, were used in order to cover a wide dynamic range, which extends from microscopic (10(-13) s) to mesoscopic (10(-9) s) times. Moreover, neutron diffraction experiments with polarization analysis were also carried out in order to characterize the structural features of the sample investigated. Fast oscillations of increasing amplitude with temperature and pi-flips are identified for phenylene rings motions. Due to the structural disorder characteristic of the amorphous state, both molecular motions display a broad distribution of relaxation times, which spreads over several orders of magnitude. Based on the results obtained, we propose a model for phenylene rings dynamics, which combines the two kinds of molecular motions identified. This model nicely describes the neutron scattering results in the whole dynamic range investigated.     

Water dynamics in graphite oxide investigated with neutron scattering

Graphite oxide is an inorganic multilayer system that preserves the layered structure of graphite but not the conjugated bond structure. In the past few years, detailed studies of the static structure of graphite oxide were carried out. This was mainly done by NMR investigations and led to a new structural model of graphite oxide. The layer distance of graphite oxide increases with increasing humidity level, giving rise to different spacings of the carbon layers in the range from 6 to 12 A. As a consequence, different types of motions of water and functional groups appear. Information about the mobility of the water molecules is not yet complete but is crucial for the understanding of the structure of the carbon layers as well as the intercalation process. In this paper, the hydration- and temperature-dependent dynamic behavior of graphite oxide will be investigated by quasielastic neutron scattering using the time-of-flight spectrometer NEAT at the Hahn-Meitner-Institut Berlin. The character of the embedded water does not change over a wide range of hydration levels. Especially the interlayer water remains tightly bound and does not show any translational motion. In samples with excess water, however, the water is also distributed in noninterlayer voids, leading to the observation of additional motions of bulklike or confined water. The dynamic behavior of hydrated graphite oxide can be described by a consistent model that combines two two-site jump motions for the motions of the water molecules and the motions of OH groups.     

Geometry of phenylene motion in polycarbonate from NMR spectroscopy and neutron scattering

In view of the importance of molecular dynamics in condensed matter both time scale and geometry of such processes should be determined experimentally. Whereas many techniques are available for the former, only NMR spectroscopy and neutron scattering can provide detailed information on the latter. Because of the different time scales of the dynamics, which the two techniques can detect best, direct comparisons of probing the geometry of the dynamics in the same system are scarce. Here we present such a comparison for the complex rotational motion of the phenylene groups in amorphous polycarbonate based on published (2)H NMR and newly recorded (13)C NMR data covering a wide temperature range, and recent quasielastic neutron scattering (QENS) data. We show that the results of the two techniques are in remarkable agreement, provided the data are consistently analyzed. No evidence is found for additional motions characterized by 90 degrees flips recently deduced from QENS data alone. Instead, the phenylene motion in the glassy state displays a broad heterogeneous distribution of rotational angles, about 80 degrees in width, centered at a flip angle of 180 degrees , which stays essentially constant over a wide temperature range. Thus, the phenylene motion that can consistently be observed in NMR and neutron scattering experiments is sensitive to the local packing.     

Coherent dynamics of meta-toluidine investigated by quasielastic neutron scattering

The coherent dynamics of a typical fragile glass former, meta-toluidine, was investigated at the molecular level using quasielastic neutron scattering, with time-of-flight and neutron spin echo spectrometers. It is well known that the static structure factor of meta-toluidine shows a prepeak originating from clustering of the molecules through hydrogen bonding between the amine groups. The dynamics of meta-toluidine was measured for several values of the wavevector transfer Q, which is equivalent to an inverse length scale, in a range encompassing the prepeak and the structure factor peak. Data were collected in the temperature range corresponding to the liquid and supercooled states, down to the glass transition. At least two dynamical processes were identified. This paper focuses on the slowest relaxation process in the system, the α-relaxation, which was found to scale with the macroscopic shear viscosity at all the investigated Q values. No evidence of "de Gennes" narrowing associated with the prepeak was observed, in contrast with what happens at the Q value corresponding to the interparticle distance. Moreover, using partially deuterated samples, the dynamics of the clusters was found to be correlated to the single-particle dynamics of the meta-toluidine molecules.     

Intense quasielastic neutron scattering of 4,4'-diethyoxyazoxybenzene and its connection with the inelastic neutron scattering spectrum

This is a continuation of a previous study of the odd-even effect for compounds of the series of 4,4'-di-n-alkyloxyazoxybenzenes. The reduction of the elastic component of the neutron scattering spectra (the elasticity depression), studied earlier at constant ΔT from the clearing point, has now been studied at constant temperature. The ethyoxy member of the series shows an exceptionally large elasticity depression; this is interpreted as evidence of a small steric hindrance for molecular motions due to the high nematic order parameter. This statement has been corroborated by the inelastic neutron scattering measurements for solid compounds of the series.     

Water motion in reverse micelles studied by quasielastic neutron scattering and molecular dynamics simulations

Motion of water molecules in Aerosol OT [sodium bis(2-ethylhexyl) sulfosuccinate, AOT] reverse micelles with water content w(0) ranging from 1 to 5 has been explored both experimentally through quasielastic neutron scattering (QENS) and with molecular dynamics (MD) simulations. The experiments were performed at the energy resolution of 85 microeV over the momentum transfer (Q) range of 0.36-2.53 A(-1) on samples in which the nonpolar phase (isooctane) and the AOT alkyl chains were deuterated, thereby suppressing their contribution to the QENS signal. QENS results were analyzed via a jump-diffusion/isotropic rotation model, which fits the results reasonably well despite the fact that confinement effects are not explicitly taken into account. This analysis indicates that in reverse micelles with low-water content (w(0)=1 and 2.5) translational diffusion rate is too slow to be detected, while for w(0)=5 the diffusion coefficient is much smaller than for bulk water. Rotational diffusion coefficients obtained from this analysis increase with w(0) and are smaller than for bulk water, but rotational mobility is less drastically reduced than translational mobility. Using the Faeder/Ladanyi model [J. Phys. Chem. B 104, 1033 (2000)] of reverse micelle interior, MD simulations were performed to calculate the self-intermediate scattering function F(S)(Q,t) for water hydrogens. Comparison of the time Fourier transform of this F(S)(Q,t) with the QENS dynamic structure factor S(Q,omega), shows good agreement between the model and experiment. Separate intermediate scattering functions F(S) (R)(Q,t) and F(S) (CM)(Q,t) were determined for rotational and translational motion. Consistent with the decoupling approximation used in the analysis of QENS data, the product of F(S) (R)(Q,t) and F(S) (CM)(Q,t) is a good approximation to the total F(S)(Q,t). We find that the decay of F(S) (CM)(Q,t) is nonexponential and our analysis of the MD data indicates that this behavior is due to lower water mobility close to the interface and to confinement-induced restrictions on the range of translational displacements. Rotational relaxation also exhibits nonexponential decay. However, rotational mobility of O-H bond vectors in the interfacial region remains fairly high due to the lower density of water-water hydrogen bonds in the vicinity of the interface.     

Orientation and relaxation of polymer–clay solutions studied by rheology and small-angle neutron scattering

The influence of shear on viscoelastic solutions of poly(ethylene oxide) (PEO) and clay [montmorillonite, i.e., Cloisite NA+ (CNA)] was investigated with rheology and small-angle neutron scattering (SANS). The steady-state viscosity and SANS were used to measure the shear-induced orientation and relaxation of the polymer and clay platelets. Anisotropic scattering patterns developed at much lower shear rates than in pure clay solutions. The scattering anisotropy saturated at low shear rates, and the CNA clay platelets aligned with the flow, with the surface normal parallel to the gradient direction. The cessation of shear led to partial and slow randomization of the CNA platelets, whereas extremely fast relaxation was observed for laponite (LRD) platelets. These PEO–CNA networklike solutions were compared with previously reported PEO–LRD networks, and the differences and similarities, with respect to the shear orientation, relaxation, and polymer–clay interactions, were examined. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3102–3112, 2004     

Quasielastic neutron scattering and relaxation processes in proteins: analytical and simulation-based models

The present article gives an overview of analytical and simulation approaches to describe the relaxation dynamics of proteins. Particularly emphasised are recent developments of theoretical models, such as fractional Brownian dynamics. The latter connects dynamical events seen on the pico- to nanosecond time scale, accessible to quasielastic neutron scattering, and functional dynamics of proteins on much longer time scales.     

Diffusive solvent dynamics in a polymer gel electrolyte studied by quasielastic neutron scattering

A quasielastic neutron scattering study has been performed on a polymer gel electrolyte consisting of lithium perchlorate dissolved in ethylene carbonate/propylene carbonate and stabilized with poly(methyl methacrylate). The dynamics of the solvent, which is crucial for the ion conduction in this system, was probed using the hydrogen/deuterium contrast variation method with nondeuterated solvent and a deuterated polymer matrix. Two relaxation processes of the solvent were studied in the 10-400 microeV range at different temperatures. From analysis of the momentum transfer dependence of the processes we conclude that the faster process ( approximately 100 microeV) is related to rotational diffusion of the solvent and the slower process ( approximately 10 microeV) to translational diffusion of the solvent. The translational diffusion is found to be similar to the diffusion in the corresponding liquid electrolyte at short distances, but geometrically constrained by the polymer matrix at distances beyond approximately 5 A. The study indicates that the hindered diffusion of the solvent on a length scale of the polymer network interchain distance ( approximately 5-20 A) is sufficient to explain the reduced macroscopic diffusivity and ion conductivity of the gel electrolyte compared to the liquid electrolyte.     

Solvent and lipid dynamics of hydrated lipid bilayers by incoherent quasielastic neutron scattering

The microscopic dynamics of the planar, multilamellar lipid bilayer system 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) has been investigated using quasielastic neutron scattering. The DMPC was hydrated to a level corresponding to approximately nine water molecules per lipid molecule. Selective deuteration has been used to separately extract the dynamics of the water, the acyl chains, and the polar head groups from the strong incoherent scattering of the remaining hydrogen atoms. Furthermore, the motions parallel and perpendicular to the bilayers were probed by using two different sample orientations relative to the incident neutron beam. For both sample orientations, the results showed an onset of water motions at 260 K on the experimental time scale of about 100 ps. From lack of wave-vector dependence of the onset temperature for water motions, it is evident that the observed water dynamics is of mainly rotational character at such low temperatures. At 290 K, i.e., slightly below the gel-to-liquid transition around 295 K, the nature of the water dynamics had changed to a more translational character, well described by a jump-diffusion model. On the limited experimental time and length (about 10 A) scales, this jump-diffusion process was isotropic, despite the very anisotropic system. The acyl chains exhibited a weak onset of anharmonic motions already at 120 K, probably due to conformational changes (trans-gauche and/or syn-anti) in the plane of the lipid bilayers. Other anharmonic motions were not observed on the experimental time scale until temperature had been reached above the gel-to-liquid transition around 295 K, where the acyl chains start to show more substantial motions.     

Deswelling of microfibril bundles in drying wood studied by small-angle neutron scattering and molecular dynamics

Cellulose - Structural changes of cellulose microfibrils and microfibril bundles in unmodified spruce cell wall due to drying in air were investigated using time-resolved small-angle neutron...     

Strain and temperature accelerated relaxation in polycarbonate

The nonlinear viscoelastic behavior of glassy polymers and its relationship to ductile yielding is studied by single- and double-step stress relaxation experiments. In the latter case a small stress relaxation step is superimposed on a specimen at an elevated state of temperature or strain. The results show that the changes in the relaxation behaviors in the two cases closely parallel each other. The relaxation behavior at strains near yield closely approximates that at low strain but near Tg. The small strain relaxation response can be described well by a Kohlrausch-Williams-Watts (KWW) type function. The interpretation of these data in terms of a coupling model which includes the KWW form is discussed.     

Study of statics and dynamics of hydrogen bonds using neutron scattering

The various observables which can be derived using neutron scattering in hydrogen-bonded systems are reviewed and a sample of experiments dealing with those observables is also presented. The relevance of the non-localized behaviour of the hydrogen wave function is also discussed.     

Small angle neutron scattering and its application in battery systems

Small angle neutron scattering is a powerful, non-destructive technique that can provide both structural and compositional information. Recently, it has been applied to the field of battery research and has helped elucidate some of the phenomena that are traditionally difficult to probe, including lithiation mechanisms, solid electrolyte interface formation/composition, and electrode microstructure. Specific components of interest can be selectively probed through the application of targeted experiments, contrast variation, and specific composition/structural models gained from complementary data from other analytical techniques.     

The dynamics of ring rotation in ferrocene,nickelocene and ruthenocene by incoherent quadi-elastic neutron scattering

Incoherent quasi-elastic neutron scattering has been used to study the reorientational motions of the cyclopentadienyl rings in ferrocene, nickelocene and ruthenocene. The results for ferrocene show that the activation energy for ring rotation drops above the 164 K phase transition to 4.4 ± 0.5 kJ mol^?1 (which is approximately half its low temperature value) but the rings still appear to jump between only five orientations on the observable time scale. At room temperature, the rings in nickelocene appear to behave the same as in ferrocene but in ruthenocene they reorientate much less frequently and resemble those in ferrocene below 164 K.     

Plasticizer effect on the dynamics of polyvinylchloride studied by dielectric spectroscopy and quasielastic neutron scattering

We have studied the influence of plasticization on the microscopic dynamics of a glass-forming polymer. For this purpose we studied polyvinylchloride (PVC) with and without the commercially used plasticizer dioctylphthalate (DOP). We used dielectric spectroscopy and inelastic neutron scattering employing the neutron spin echo (NSE) technique. For both kinds of spectra the alpha relaxation could be consistently described by a model involving a distribution of individual relaxations of the Kohlrausch type. In contrast to earlier studies it turned out that an asymmetric distribution is necessary to fit the data at the lower temperatures investigated here. The shape parameters of the distribution (width, skewness) for PVC and PVC/DOP turned out to coincide when the characteristic relaxation times were the same. This means that the plasticizer only induces a remapping of the temperature dependence of the alpha relaxation. Comparison of NSE spectra S(Q,t)S(Q) at different scattering vectors Q gave the result that the slowing down at the structure factor peak Q(max) is surprisingly small for PVC while it is in the normal range for PVC/DOP.     

Molecular dynamics of glucose in solution: a quasielastic neutron scattering study

The molecular dynamics of glucose dissolved in heavy water have been investigated at 280 K by the technique of quasielastic neutron scattering. The scattering was described by a dynamic structure factor that accounts for decoupled diffusive jumps and free rotational motions of the glucose molecules. With increasing glucose concentration, the diffusion constant decreases by a factor five and the time between jumps increases considerably. Our observations validate theoretical predictions concerning the impact of concentration on the environment of a glucose molecule and the formation of cages made by neighboring glucose molecules at higher concentrations.