Surface Energy and Surface Proton Order of Ice Ih

Ice Ih is comprised of orientationally disordered water molecules giving rise to positional disorder of the hydrogen atoms in the hydrogen bonded network of the lattice. Here we arrive at a first principles determination of the surface energy of ice Ih and suggest that the surface of ice is significantly more proton ordered than the bulk. We predict that the proton order-disorder transition, which occurs in the bulk at similar to 72 K, will not occur at the surface at any temperature below surface melting. An order parameter which defines the surface energy of ice Ih surfaces is also identified.

Simultaneous extraction of order parameters and orientational distribution fuctions from 31[superscript]P NMR spectra of magnetically partially oriented phospholipid bilayers

Order parameter profiles extracted from the NMR spectra of model membranes are a valuable source of information about their structure and molecular motions. To al1alyze powder spectra the de-Pake-ing (numerical deconvolution) ~echnique can be used, but it assumes a random (spherical) dist.ribution of orientations in the sample. Multilamellar vesicles are known to deform and orient in the strong magnetic fields of NMR magnets, producing non-spherical orientation distributions. A recently developed technique for simultaneously extracting the anisotropies of the system as well as the orientation distributions is applied to the analysis of partially magnetically oriented 31p NMR spectra of phospholipids. A mixture of synthetic lipids, POPE and POPG, is analyzed to measure distortion of multilamellar vesicles in a magnetic field. In the analysis three models describing the shape of the distorted vesicles are examined. Ellipsoids of rotation with a semiaxis ratio of about 1.14 are found to provide a good approximation of the shape of the distorted vesicles. This is in reasonable agreement with published experimental work. All three models yield clearly non-spherical orientational distributions, as well as a precise measure of the anisotropy of the chemical shift. Noise in the experimental data prevented the analysis from concluding which of the three models is the best approximation. A discretization scheme for finding stability in the algorithm is outlined

Electro-optical properties of liquid crystal copolymers and their relationship to structural order

A range of side chain liquid crystal copolymers have been prepared using mesogenic and non-mesogenic units. It is found that high levels of the non-mesogenic moieties may be introduced without completely disrupting the organization of the liquid crystal phase. Incorporation of this comonomer causes a marked reduction in the glass transition temperature (Tg), presumably as a result of enhanced backbone mobility and a corresponding lowering of the nematic transition temperature, thereby restricting the temperature range for stability of the liquid crystal phase. The effect of the interactions between the various components of these side-chain polymers on their electro-optic responses is described. Infrared (i.r.) dichroism measurements have been made to determine the order parameters of the liquid crystalline side-chain polymers. By identifying a certain band (CN stretching) in the i.r. absorption spectrum, the order parameter of the mesogenic groups can be obtained. The temperature and composition dependence of the observed order parameter are related to the liquid crystal phase transitions and to the electro-optic response. It is found that the introduction of the non-mesogenic units into the polymer chain lowers the threshold voltage of the electro-optic response over and above that due to the reduction in the order parameter. The dynamic electro-optic responses are dominated by the temperature-dependent viscosity and evidence is presented for relaxation processes involving the polymer backbone which are on a time scale greater than that for the mesogenic side-chain units.

First-order-like transition in salt-induced macroion-polyelectrolyte desorption

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Mixed order parameters, accidental nodes and broken time reversal symmetry in organic superconductors: a group theoretical analysis

We present a group theoretical analysis of several classes of organic superconductor. We predict that highly frustrated organic superconductors, such as K-(ET)(2)Cu-2(CN)(3) (where ET is BEDT-TTF, bis(ethylenedithio) tetrathiafulvalene) and beta'-[Pd(dmit)(2)](2)X, undergo two superconducting phase transitions, the first from the normal state to a d-wave superconductor and the second to a d + id state. We show that the monoclinic distortion of K-(ET)(2)Cu(NCS)(2) means that the symmetry of its superconducting order parameter is different from that of orthorhombic-K-(ET)(2)Cu[N(CN)(2)] Br. We propose that beta'' and theta phase organic superconductors have d(xy) + s order parameters.

Variables governing the dynamics of attacker-defender systems in team sport

This project was a step forward in the examination and identification of key variables on the perception, decision making and action of team sport athletes through theoretical insights provided by the ecological dynamics perspective. The methodology drew on experiential knowledge of elite coaches to drive further empirical investigation into the specific task, environmental and personal constraints that shape the behaviour of athletes in specific performance contexts. The thesis has provided an effective rationale for further investigation into the emergent perception, decision making and action demanded of athletes in these unpredictable, fluent, fast-paced environments.

Decision making in social neurobiological systems modeled as transitions in dynamic pattern formation

Extant models of decision making in social neurobiological systems have typically explained task dynamics as characterized by transitions between two attractors. In this paper, we model a three-attractor task exemplified in a team sport context. The model showed that an attacker–defender dyadic system can be described by the angle x between a vector connecting the participants and the try line. This variable was proposed as an order parameter of the system and could be dynamically expressed by integrating a potential function. Empirical evidence has revealed that this kind of system has three stable attractors, with a potential function of the form V(x)=−k1x+k2ax2/2−bx4/4+x6/6, where k1 and k2 are two control parameters. Random fluctuations were also observed in system behavior, modeled as white noise εt, leading to the motion equation dx/dt = −dV/dx+Q0.5εt, where Q is the noise variance. The model successfully mirrored the behavioral dynamics of agents in a social neurobiological system, exemplified by interactions of players in a team sport.

Solute induced liquid crystalline behaviour of a quaternary ammonium salt and its application to structure determination

A new liquid crystalline phase, induced by the addition of small amounts of a non-mesogenic solute (such as dimethyl sulphoxide or methyl iodide) to a quaternary ammonium salt, N-methyl-N,N,N-trioctadecylammonium iodide (MTAI), has been detected by NMR and optical microscopic studies. In some cases, there is a coexistence of nematic and smectic phases. Information on the ordering of the phases in the magnetic field of the spectrometer has been derived from NMR spectra of a dissolved molecule, C-13-enriched methyl iodide. The low order parameter of the pure thermotropic nematic phase of the salt provides first-order spectra of the dissolved oriented molecules. Analyses of spectra of cis,cis-mucononitrile exemplifies the utility of the MTAI nematic phase in the determination of structural parameters of the solute.

Cluster model of the glass transition

A cluster model of the glass transition has been developed, treating the relative size of the cluster as an order parameter. The model accounts for some of the features of the glass transition.

NMR Investigations on Di- and Tri-Azanaphthalenes Oriented in Liquid Crystals

Proton NMR spectra of 1,3-diazanaphthalene and 1,2,4-triazanaphthalene have been investigated in the nematic phase of three liquid crystals. The spectral analysis provided direct dipole-dipole couplings which have been used to derive the molecular structure. Geometry of the phenyl ring in both the molecules deviates from the regular hexagonal structure. Signs of the order parameter of the largest magnitude are opposite in liquid crystals with positive diamagetic anisotropies.

Mean-field results of a lattice-gas model of multilayer adsorption

A lattice-gas model of multilayer adsorption has been solved in the mean-field approximation by a different numerical method. Earlier workers obtained a single solution for all values of temperature and pressure. In the present work, multiple solutions have been obtained in certain regions of temperature and pressure which give rise to bysteresis in the adsorption isotherm. In addition, we have obtained a parameter which behaves like an order parameter for the transition. The potential-energy function shows a double minimum in the region of bysteresis and a single maximum elsewhere.

Esr study of (SO4)2- dynamics in relation to the ferroelectric phase transition in ammonium sulfate

Ferroelectric phase transition in ammonium sulfate has been studied by ESR of CrO43- radical substituting for SO42- ion in (NH4)2SO4. In addition to discontinuous changes at Tc, certain continuous changes are observed in ESR parameters of this probe below Tc, which reflect the role of the sulfate ion in the phase transition. A microscopic mechanism of the phase transition is proposed and discussed in terms of the change of orientation of the sulfate tetrahedron through a finite angle. The degree of the change of orientation below Tc is thought to be the possible order parameter of the phase transition.

Structure and dynamics of two-dimensional sheared granular flows

The structure and dynamics of the two-dimensional linear shear flow of inelastic disks at high area fractions are analyzed. The event-driven simulation technique is used in the hard-particle limit, where the particles interact through instantaneous collisions. The structure (relative arrangement of particles) is analyzed using the bond-orientational order parameter. It is found that the shear flow reduces the order in the system, and the order parameter in a shear flow is lower than that in a collection of elastic hard disks at equilibrium. The distribution of relative velocities between colliding particles is analyzed. The relative velocity distribution undergoes a transition from a Gaussian distribution for nearly elastic particles, to an exponential distribution at low coefficients of restitution. However, the single-particle distribution function is close to a Gaussian in the dense limit, indicating that correlations between colliding particles have a strong influence on the relative velocity distribution. This results in a much lower dissipation rate than that predicted using the molecular chaos assumption, where the velocities of colliding particles are considered to be uncorrelated.

Coexistence curve of acetonitrile and cyclohexane liquid system

The paper reports a detailed determination of the coexistence curve for the binary liquid system acetonitrile+cyclohexane, which have very closely matched densities and the data points get affected by gravity only for t=(Tc−T)/ Tc[approximately-equal-to]10−6. About 100 samples were measured over the range 10−6

Phase transitions in (NH4)2SO4 and (NH4)2SO4---K2SO4 mixed crystals as studied by EPR of CrO3- radicals

A study of the phase transitions in (NH4)2SO4 and (NH4)2SO4---K2SO4 mixed crystals by EPR of the CrO3- ion is reported. The results indicate a bilinear coupling of the order parameter with spontaneous polarization and a crossover from a discontinuous to a continuous nature of the phase transition in mixed crystals.