Shear mechanical anisotropy of side chain liquid-crystal elastomers: Influence of sample preparation

We study the mechanical anisotropy of a series of uniaxial side chain nematic elastomers prepared with the same chemical composition but with different preparation protocols. For all the compounds, the experiments performed as a function of temperature show no discontinuity in both G' _// and G' _⊥ (the labels // and ⊥ stand for the director parallel, respectively perpendicular to the shear displacement) around the nematic-isotropic (N-I) phase transition temperature determined by DSC. They also all show a small decrease in G' _// starting at temperatures well above this temperature (from ∼ 4^° C to ∼ 20^° C depending on the compound studied) and leading to a small hydrodynamic value of the G' _⊥/G' _// ratio. The measurements taken as a function of frequency show that the second plateau in G' _// and the associated dip in G _//” expected from dynamic semi-soft elasticity are not observed. These results can be described by the de Gennes model, which predicts small elastic anisotropy in the hydrodynamic and linear regimes. They correspond to the behavior expected for compounds beyond the mechanical critical point, which is consistent with the NMR and specific heat measurements taken on similar compounds. We also show that a reduction in the cross-linking density does not change the non-soft character of the mechanical response. From the measurements taken as a function of frequency at several temperatures we deduce that the time-temperature superposition method does not apply. From these measurements, we also determine the temperature dependence of the longest relaxation time τ_E of the network for the situations where the director is either parallel or perpendicular to the shear velocity. Finally, we discuss the influence on the measurements of the mechanical constraint associated with the fact that the samples cannot change their shape around the pseudo phase transition, because of their strong adherence on the sample-bearing glass slides.     

Influence of the nematic order on the rheology and conformation of stretched comb-like liquid crystalline polymers

We have studied the rheology and the conformation of stretched comb-like liquid-crystalline polymers. Both the influence of the comb-like structure and the specific effect of the nematic interaction on the dynamics are investigated. For this purpose, two isomers of a comb-like polymetacrylate polymer, of well-defined molecular weights, were synthesized: one displays a nematic phase over a wide range of temperature, the other one has only an isotropic phase. Even with high degrees of polymerization N, between 40 and 1000, the polymer chains studied were not entangled. The stress-strain curves during the stretching and relaxation processes show differences between the isotropic and nematic comb-like polymers. They suggest that, in the nematic phase, the chain dynamics is more cooperative than for a usual linear polymer. Small-angle neutron scattering has been used in order to determine the evolution of the chain conformation after stretching, as a function of the duration of relaxation t _r. The conformation can be described with two parameters only: , the global deformation of the polymer chain, and p, the number of statistical units of locally relaxed sub-chains. For the comb-like polymer, the chain deformation is pseudo-affine: is always smaller than (the deformation ratio of the whole sample). In the isotropic phase, has a constant value, while pincreases as tr. This latter behavior is not that expected for non-entangled chains, in which p varies as t _r ^1/2 (Rouse model). In the nematic phase, decreases as a stretched exponential function of t _r, while p remains constant. The dynamics of the comb-like polymers is discussed in terms of living clusters from which junctions are produced by interactions between side chains. The nematic interaction increases the lifetime of these junctions and, strikingly, the relaxation is the same at all scales of the whole polymer chain. Received 5 May 1999 and Received in final form 18 October 1999     

Thermodynamics and transport in an active Morse ring chain

We investigate the stochastic dynamics of an one-dimensional ring with N self-driven Brownian particles. In this model neighboring particles interact via conservative Morse potentials. The influence of the surrounding heat bath is modeled by Langevin-forces (white noise) and a constant viscous friction coefficient γ. The Brownian particles are provided with internal energy depots which may lead to active motions of the particles. The depots are realized by an additional nonlinearly velocity-dependent friction coefficient γ ₁(v) in the equations of motions. In the first part of the paper we study the partition functions of time averages and thermodynamical quantities (e.g. pressure) characterizing the stationary physical system. Numerically calculated non-equilibrium phase diagrams are represented. The last part is dedicated to transport phenomena by including a homogeneous external force field that breaks the symmetry of the model. Here we find enhanced mobility of the particles at low temperatures. Received 21 July 2001     

Collapse transitions of a periodic hydrophilic hydrophobic chain

We study a single self avoiding hydrophilic hydrophobic polymer chain, through Monte-Carlo lattice simulations. The affinity of monomer i for water is characterized by a (scalar) charge , and the monomer-water interaction is short-ranged. Assuming incompressibility yields an effective short ranged interaction between monomer pairs (i,j), proportional to . In this article, we take (resp. ()) for hydrophilic (resp. hydrophobic) monomers and consider a chain with (i) an equal number of hydro-philic and -phobic monomers (ii) a periodic distribution of the along the chain, with periodicity 2p. The simulations are done for various chain lengths N, in d=2 (square lattice) and d=3 (cubic lattice). There is a critical value p _c (d,N) of the periodicity, which distinguishes between different low temperature structures. For p >p _c , the ground state corresponds to a macroscopic phase separation between a dense hydrophobic core and hydrophilic loops. For p <p _c (but not too small), one gets a microscopic (finite scale) phase separation, and the ground state corresponds to a chain or network of hydrophobic droplets, coated by hydrophilic monomers. We restrict our study to two extreme cases, and to illustrate the physics of the various phase transitions. A tentative variational approach is also presented. Received: 10 March 1998 / Received in final form: 25 June 1998 / Accepted: 1st July 1998     

High-pressure Raman spectra of L-isoleucine crystals

Raman spectroscopy investigations of L-isoleucine crystals under high pressures have been carried out up to 7.3 GPa. From this study it was possible to observe modifications on bands associated to both rocking vibrations of r(NH₃⁺) and r(CO₂⁻) as well as to lattice modes at about 2.3 and 5.0 GPa. These modifications were correlated to either conformational change of molecules or to a solid–solid phase transition undergone by the crystals involving the hydrogen bonds that maintain the molecules held in the unit cell. A comparison with a few results on other amino acid crystals is also given.     

Competition of disorder and interchain hopping in a two-chain Hubbard model

We study the interplay of Anderson localization and interaction in a two chain Hubbard ladder allowing for arbitrary ratio of disorder strength to interchain coupling. We obtain three different types of spin gapped localized phases depending on the strength of disorder: a pinned 4k _F Charge Density Wave (CDW) for weak disorder, a pinned 2k _F CDW^π for intermediate disorder and two independently pinned single chain 2k _F CDW for strong disorder. Confinement of electrons can be obtained as a result of strong disorder or strong attraction. We give the full phase diagram as a function of disorder, interaction strength and interchain hopping. We also study the influence of interchain hopping on localization length and show that localization is enhanced by a small interchain hopping but suppressed by a large interchain hopping. Received 6 April 2001     

Structures and reactions of biomolecular ions produced with electrospray ionization

Photo-induced reaction of [Fe(III)-protoporphyrin]⁺ (hemin⁺) ions solvated with dimethylsulfoxide (DMSO) is investigated by using a tandem mass spectrometer with electrospray ionization. We measure the photodissociation yields of mass-selected hemin⁺(DMSO)_n clusters for n = 0-3. The mass spectra of the fragment ions show the -cleavage of carboxymethyl groups in addition to the evaporation of solvent molecules. Yield of the -cleavage reaction is found to depend strongly on the excitation energy and the number of solvent molecules. We also examine photo-induced reactions of multiply-charged cytochrome c ions, (M + nH)^{n +} ( n = 9-17). Photoionization is found to be the dominant process for the lower charged states ( n = 9-12) and its yield decreases rapidly with increasing the charge. The photoionization is ascribed to the emission of electron by multiphoton excitation of heme under the influence of Coulomb attractive potential arising from the charges in the polypeptide chain. Model calculations of the Coulomb potential suggest that the structure of the polypeptide chain is completely elongated.     

3d D lifetime in laser cooled Ca : Influence of cooling laser power

We have measured the lifetime of the metastable 3D _5/2 level in Ca⁺ using the “quantum jump" technique on a single stored and laser cooled ion in a linear Paul trap. We found a linear dependence of the measured decay rate on the power of the laser which repumps the ions from the long lived 3D _3/2 level. This can be explained by off-resonant depletion of the 3D _5/2 level. The proper lifetime of this level is obtained by a linear extrapolation of the measured lifetime to zero laser power. We obtain 1100(18) ms in agreement with theoretical calculations. The observed systematic change of the decay rate resolves discrepancies between earlier experiments in which this effect had not been considered. Measurements on a linear chain of 10 laser cooled ions showed unexpected frequent coincidences of quantum jumps within our observation time of 20 ms. This indicates a so far unexplained correlation between the ions in the chain at large distances. Received 3 March 1999     

A small-angle X-ray scattering study of the isotropic and nematic phases of V2O5 suspensions

We report small-angle X-ray scattering experiments performed in both the isotropic and nematic phases of aqueous V₂O₅ suspensions. We show that the scattering in the isotropic phase can be well described in the whole accessible q-range by only considering the form factor of non-interacting ribbons. We investigate the influence of concentration and pH on the dimensions of V₂O₅ ribbons and show that these parameters do not have any significant effect, as long as the system stays well within the chemical stability domain of the ribbons. We then show that nematic single domains display an anisotropic small-angle scattering pattern, even at scattering vectors small compared to that at which a characteristic correlation peak is observed. This feature is expected for a nematic phase, but was rarely observed. We finally try to describe this scattering within the framework of theories developed for the structure factor of a nematic polymer, and we reach the conclusion that chain ends are certainly important to understand this pattern. Received 21 July 1999 and Received in final form 17 December 1999     

Using the full Raman depolarisation in the determination of the order parameters in liquid crystal systems

The depolarisation ratio for the Raman-active phenyl stretching mode has been measured over the whole of the mesophase range, and the orientational order parameters deduced, in the uniaxial nematic liquid crystal octylcyanobiphenyl (8CB). Linearly polarised light was incident normally on a homogeneously aligned sample and a χ² minimisation routine performed on the 360^° depolarisation ratio profile. The order parameters 〈P ₂₀₀〉 and 〈P ₄₀₀〉 , together with the differential polarisability ratio, r , are used as fitting parameters and measured as a function of temperature. Interestingly, we show that the value for r , conventionally measured in the isotropic phase and assumed to remain constant, has a clear temperature dependence, ranging from -0.032±0.008 in the isotropic phase through to -0.245±0.015 at the nematic-to-smectic A phase transition. The measured order parameters 〈P ₂₀₀〉 and 〈P ₄₀₀〉 varied from 0.35- 0.55±0.02 and 0.180- 0.245±0.02 , respectively, across the 8 ^° C wide nematic phase range. The values of both 〈P ₂₀₀〉 and 〈P ₄₀₀〉 are in excellent agreement with theory, but it is noteworthy that 〈P ₄₀₀〉 shows a much better quantitative match than has been reported in previous work. Crucially the temperature dependence of r is shown to be a contributing factor in the low 〈P ₄₀₀〉 values that have been conventionally reported from Raman scattering measurements. The potential for fitting the entire angular depolarisation ratio distribution in liquid crystalline systems that are described by more order parameters, specifically biaxial materials, is discussed.     

Mössbauer study of the vibrational anisotropy and of the light-induced population of metastable states in single-crystalline guanidinium nitroprusside

M?ssbauer studies were performed on single crystals of guanidinium nitroprusside with different orientations of their principal crystallographic axes (a, b, c) with respect to the incident radiation. The markedly anisotropic Lamb-M?ssbauer factor f _LM , i.e. f _LM ^(a) = 0.118(8), f _LM ^(b) = 0.174(8), f _LM ^(c) = 0.202(8) is in contrast to that of nitroprussides with inorganic anions. The observed anisotropy is ascribed to the anisotropic vibrational mean-square displacement of the nitroprusside anions as a whole which is due to the specific packing of both, anions and cations, as well as the very weak chemical bonding between the ions, typical only for guanidinium nitroprusside. The vibrational anisotropy of iron atoms in barium nitroprusside that has been observed by X-ray structural investigations has a different origin and therefore does not result in an anisotropic Lamb-M?ssbauer factor. We have also investigated metastable states in guanidinium nitroprusside that have been populated by means of incoherent irradiation from light-emitting diodes. With a specific orientation of the guanidinium nitroprusside single crystal a population of the metastable states up to 26% could be achieved. Populations of comparable size on lithium, sodium and potassium nitroprussides have only been reached using coherent laser irradiation. Received 15 December 1998 and Received in final form 3 March 1999     

Log-periodic oscillations for biased diffusion of a polymer chain in a porous medium

A coarse-grained off-lattice bead-spring model is used to reveal the complex dynamics of a polymer chain in a quenched porous medium in the presence of an external field B. The behavior of the mean square displacement (MSD) of the center chain bead and that of the center of mass of the chain as a function of time is studied at different values of the barrier concentration C, the field strength B and the chain length N. In a field, important information on the way in which chains move between obstacles and overcome them is gained from the MSD vs. time analysis in the directions parallel and perpendicular to the flow. Instead of a steady approach to uniform drift-like motion at low C, for sufficiently strong field B we observe logarithmic oscillations in the effective exponents describing the time dependence of the MSD along and perpendicular to field. A common nature of this phenomenon with oscillatory behavior, observed earlier for biased diffusion of tracers on random lattices, is suggested. Received 7 August 1998     

Soft modes and phonon interactions in studied by neutron scattering

The low frequency lattice dynamics and its relationship to the second order paraelectric-to-ferroelectric transition in Sn₂P₂S₆ is studied. The dispersion branches of the acoustic and lowest lying optical phonons in the a^*-c^* plane have been obtained in the ferroelectric phase, for x-polarized phonons. Close to the phase transition a considerable softening is found for the lowest optical mode (P_x), comparable to the behaviour observed in previous Raman investigations. As found previously in Sn₂P₂Se₆, a strong coupling between the TO(P_x) and TA(u_xz) phonons is observed, although, apparently, not strong enough to lead to an incommensurate phase. The soft TO(P_x) mode at the zone center is observed. The temperature dependence of its frequency and damping shows that the transition is not entirely displacive. At low temperatures an unusual apparent negative LO-TO splitting is observed which is shown to arise from the coupling of the x-polarized soft mode to the nearby z-polarized optical phonon. For comparison, the soft TO(P_x) dispersion in the a^*-b^* plane is measured in both the paraelectric and ferroelectric phases. Consistent frequency changes and LO-TO splitting are observed, revealing a significant interaction between the TA(u_yx) and LA(u_xx) acoustics branches and the TO and LO soft optic branches, respectively. In contrast, the nearby y-polarized optic branch shows almost no temperature dependence. Finally, the influence of piezoelectric effects on the limiting acoustic slopes in the ferroelectric phase is discussed. Received: 11 May 1998 / Revised and Accepted: 15 June 1998     

Polymer chain in a quenched random medium: slow dynamics and ergodicity breaking

The Langevin dynamics of a self-interacting chain embedded in a quenched random medium is investigated by making use of the generating functional method and one-loop (Hartree) approximation. We have shown how this intrinsic disorder causes different dynamical regimes. Namely, within the Rouse characteristic time interval the anomalous diffusion shows up. The corresponding subdiffusional dynamical exponents have been explicitly calculated and thoroughly discussed. For the larger time interval the disorder drives the center of mass of the chain to a trap or frozen state provided that the Harris parameter, (Δ/b ^d)N ^{2 - νd}≥1, where Δ is a disorder strength, b is a Kuhnian segment length, N is a chain length and ν is the Flory exponent. We have derived the general equation for the non-ergodicity function f (p) which characterizes the amplitude of frozen Rouse modes with an index p = 2πj/N. The numerical solution of this equation has been implemented and shown that the different Rouse modes freeze up at the same critical disorder strength Δ _c ∼ N ^{- γ} where the exponent γ ≈ 0.25 and does not depend from the solvent quality. Received 17 December 2002 Published online 23 May 2003 RID="a" ID="a"e-mail: vilgis@mpip-mainz.mpg.de     

A chiral axial next nearest neighbour xy-model for antiferroelectric liquid crystals

We describe a chiral axial next nearest neighbour xy-model to account for the various subphases exhibited by antiferroelectric liquid crystals made of chiral rod-like molecules. The assumed form of the interlayer interactions is based on physical processes which are discussed. Using a discrete model, the predicted sequence of transitions is SmA-SmC-SmC-FI_H-FI_I-FI_L-SmC ^* A, where FI stands for a ferriphase, as seen in many compounds. The ferri and SmC phases are characterized by relatively large angles between the c-vectors of successive layers and occur only when the compounds have high optical purity. The calculated field induced structures exhibit a plateau of the apparent tilt angle at , where is the tilt angle of the molecules in the ferriphase. The conoscopic figures in the presence of a field and ellipsometric parameters in the absence of a field have also been generated, which agree extremely well with the experimental results. Recent anomalous X-ray scattering studies prove the xy-character of the configurations, though the commensurate structures that are found in the ferriphase require an extension of the model to include lock-in terms. Received 23 August 1999     

Continuum light emission from sputtered species of graphite during ion beam irradiation

Light emission during sputtering of graphite targets with 1–10 keV Ne⁺, Kr⁺ and Xe⁺ beams has been investigated in the 180-600 nm wavelength range. Beside the characteristic lines of sputtered C₁ and C₁ ⁺, a continuum superimposed with a number of broad structures was observed in the 250-520 nm range, and having a maximum at 386 nm. Mass analysis of the sputtered flux confirmed the presence of negative carbon clusters C _m ^- , C₂ ^- being the dominant one. Ion beam parameters i.e. ion mass, energy, current density and ion dose were varied to identify the origin of the continuum emission. On the basis of the experimental results, it is suggested that the continuum is predominantly due to the overlapping of various band systems of sputtered C₂ with a small contribution from the heavier sputtered carbon clusters C_m (m>2). Received 24 September 1999 and Received in final form 11 February 2000     

Influence of covalence and anion symmetry on the structure of small metal hydroxide clusters: Sodium versus silver hydroxide

An ab initio study of the Na_n(OH)_n, Na_n(OH)_n-1 ⁺, Ag_n(OH)_n, and Ag_n(OH)_n-1 ⁺ clusters with n up to four is presented. The results of this study show that, in accordance with experimental observations, the sodium hydroxide clusters are almost purely ionic, while the Ag-O bond exhibits a significant covalent character. The perturbation caused by the non-spherical OH^- group relatively to an atomic anion, as well as the influence on structures and energies of the covalent character of the metal-oxygen bond are determined. The appearance of metal-metal bonds in the silver hydroxide clusters is also discussed. Finally, the theoretical results obtained on the Na-OH clusters are compared to experimental results available on the dissociation of the Na_n(OH)_n-1 ⁺ clusters. Received 9 August 1999 and Received in final form 1st December 1999     

Some structural and dynamical properties of multilamellar vesicles incorporated with propranolol

Summary Spin labelling ESR, calorimetry and³¹P NMR have been used to investigate dipalmitoyl phosphatidylcholine dispersions incorporated with propranolol which is a β-adrenoceptor blocking drug, widely used in the treatment of arrhythmy. The drug appears to enter the lipid bilayer also at the lowest concentrations and to induce a progressive fluidification of multilamellar vesicles. In fact, the presence of drug reduces the temperature of chain melting transition and the corresponding cooperation number. Furthermore the phase transitionL _β′ −P _β′ is not observable also at the lowest drug concentrations. Work presented at the First USSR-Italy Bilateral Meeting on Liquid Crystals held in Portonovo, Ancona (Italy), September 30–October 2, 1987.