Liquids in equilibrium: Beyond the hypernetted chain

Density functional techniques are used to derive a charging expression for the non-uniform density of a molecular liquid. In the atomic limit the equation reduces to an exact form due to Fixman. The theory is simplified greatly via a physical approximation that accounts for three-body correlations beyond those included in the hypernetted chain (HNC) closure of the Ornstein-Zernike (OZ) equation. The radial distribution function is obtained as a special case. The theory is tested by examining the phase behavior of two fundamental complex fluids: the homopolymer blend and diblock copolymer melts. For the former it is found, contrary to HNC theory and its molecular generalizations, that a critical temperature T_c is predicted from the structure route. This T_c scales linearly with degree of polymerization N in agreement with Flory theory. The simplest form of the theory can be considered as a way to incorporate attractive interactions within a formalism that is very similar to that of the OZ or reference interaction site model (RISM). The relevance of the theory to charged liquids is also discussed.     

Statistical theory of force-induced unzipping of DNA

The unzipping transition under the influence of external force of a dsDNA molecule has been studied using the Peyrard-Bishop Hamiltonian. The critical force F_c(T) for unzipping calculated in the constant force ensemble is found to depend on the potential parameter k which measures the stiffness associated with a single strand of DNA and on D, the well depth of the on-site potential representing the strength of hydrogen bonds in a base pair. The dependence on temperature of F_c(T) is found to be (T_D - T)^1/2 (T_D being the thermal denaturation temperature) with F_c(T_D) = 0 and F_c(0) = . We used the constant extension ensemble to calculate the average force F(y) required to stretch a base pair a y distance apart. The value of F(y) needed to stretch a base pair located far away from the ends of a dsDNA molecule is found twice the value of the force needed to stretch a base pair located at one of the ends to the same distance for y 1.0 . The force F(y) in both cases is found to have a very large value for y 0.2 compared to the critical force found from the constant force ensemble to which F(y) approaches for large values of y. It is shown that the value of F(y) at the peak depends on the value of k which measures the energy barrier associated with the reduction in DNA strand rigidity as one passes from dsDNA to ssDNA and on the value of the depth of the on-site potential. The effect of defects on the position and height of the peak in the F(y) curve is investigated by replacing some of the base pairs including the one being stretched by defect base pairs. The formation and behaviour of a loop of Y shape when one of the ends base pair is stretched and a bubble of ssDNA with the shape of an eye when a base pair far from ends is stretched are investigated.     

The effect of oxygen exposure on pentacene electronic structure

We use ultraviolet photoelectron spectroscopy to investigate the effect of oxygen and air exposure on the electronic structure of pentacene single crystals and thin films. It is found that O₂ and water do not react noticeably with pentacene, whereas singlet oxygen/ozone readily oxidize the organic compound. Also, we obtain no evidence for considerable p-type doping of pentacene by O₂ at low pressure. However, oxygen exposure lowers the hole injection barrier at the interface between Au and pentacene by 0.25 eV, presumably due to a modification of the Au surface properties.     

Frustration between syn- and anticlinicity in mixtures of chiral and non-chiral tilted smectic-C-type liquid crystals

We study the effects of mixing ferroelectric and antiferroelectric liquid-crystal compounds (FLCs and AFLCs) when the former are strictly synclinic and the latter strictly anticlinic, i.e. one mixture component exhibits only SmC* and the other only SmC a* as tilted phase. Three different paths between syn- and anticlinicity were detected: transition directly between SmC* and SmC a*, transition via the SmC_β* and SmC_γ* subphases, or by “escaping” the clinicity frustration by reducing the tilt to zero, i.e. the SmA* phase is extended downwards in temperature, separating SmC* from SmC a* in the phase diagram. The most common path is the one via the subphases, demonstrating that these phases appear as a result of frustration between syn- and anticlinic and, consequently, between syn- and antipolar order. For assessing the role of chirality, we also replaced the FLC with non-chiral synclinics. With one of the AFLCs, the route via supbhases was detected even in this case, suggesting that chirality --although necessary-- does not have quite the importance that has previously been attributed to the appearance of the subphases. The path chosen in the mixture study seemed to be determined mainly by the synclinic component, the subphase induction occurring only when the SmA*-SmC* transition was second order.     

Quantitative experimental determination of the Landau-potential of chiral enantiomer doped ferroelectric liquid crystals

The full Landau potential was determined for a ferroelectric liquid crystal doped with varying concentrations of the chiral dopant R1011 and its enantiomer S1011. A multi-curve fitting procedure using temperature and electric field dependent tilt angle and polarization data was employed to the generalized Landau model of ferroelectric liquid crystals. From this analysis the three Landau coefficients as well as the polarization-tilt coupling parameters were obtained as a function of dopant concentration and configuration. It is shown that the two most varied parameters are those of the first Landau coefficient α and the (chiral) linear polarization-tilt coupling constant C. The effect on the first Landau term is equivalent for the two dopants of opposite handedness indicating its achiral nature, while the effect on the (chiral) bilinear coupling term differs for the R1011 and S1011 dopant, increasing and decreasing the coupling between tilt and polarization respectively. This difference in the bilinear coupling term quantifiably evidences that the R1011 dopant increases and S1011 dopant reduces the inherent chirality in this system.     

Molecular multivalent electrolytes: microstructure and screening lengths

We study small rod-like molecular electrolytes solutions with their corresponding atomic counterions. The asymptotic length scales (decay length and wavelength) of the structural correlations are analyzed using the formalism of the dressed interaction site theory (DIST). The correlation functions are determined using the reference interaction site model equation complemented with a mixed approach in which the hypernetted-chain closure is used for the repulsive interactions, and the mean spherical approximation is used for the attractive interactions. The results from this scheme are in good agreement with the Monte Carlo computer simulations reported here. The asymptotic properties of the correlation functions of this molecular system are compared against those corresponding to two related simple (atomic) electrolyte models. The main conclusion is that the molecular structure of the ions lowers by two orders of magnitude the concentration at which the transition from monotonic to oscillatory decay occurs.     

Transport and sedimentation of solid particles in Bénard hexagonal cells

The motion of particles moving under gravity in the velocity field of a liquid in a Bénard hexagonal cell is studied experimentally and numerically for Stokes flow conditions. We then explain the settlement of particles in the centers of cells to form a regular quincunx. It is found that sedimentation also occurs preferentially along the lines connecting the centers of adjacent cells to form a triangle deposition tessellation. Finally, it is explained why particles occupy the central part of each convective cell while the peripheral part of the cell quickly becomes limpid. Numerical results are in agreement with the experimental observations of Bénard and those of the present study.     

Weak segregation theory and non-conventional morphologies in the ternary ABC triblock copolymers

The statistical theory of microphase separation in the ternary ABC triblock copolymers is presented and the corresponding phase diagrams are built both for the linear and miktoarm copolymers. For this purpose the Leibler weak segregation theory in molten diblock copolymers is generalized to multi-component monodisperse block copolymers with due regard for the 2nd shell harmonics contributions defined in the paper. The Hildebrand approximation for the χ-parameters is used. The physical meaning of this and alternative choices for the χ-parameters is discussed. The symmetric A_fB_1-2fC_f copolymers with the middle block non-selective with respect to the side ones are shown to undergo the continuous ODT not only into the lamellar phase but also, instead, into various non-conventional cubic phases (depending on the middle block composition it could be the simple cubic, face-centered cubic or non-centrosymmetric phase, which reveals the symmetry of I4₁ 32 space group No. 214 first predicted to appear in molten block copolymers). For asymmetric linear ABC copolymers a region of compositions is found where the weakly segregated gyroid (double gyroid) phase exists between the planar hexagonal and lamellar or one of the non-conventional cubic phases up to the very critical point. In contrast, the miktoarm (star) ABC block copolymers with one of its arm non-selective with respect to the two others are shown to reveal a pronounced tendency towards strong segregation, which is preceded by increase of stability of the conventional BCC phase and a peculiar weakly segregated BCC phase (BCC₃), where the dominant harmonics belong to the 3rd coordination sphere of the reciprocal lattice. The validity region of the developed theory is discussed and outlined in the composition triangles both for linear and miktoarm copolymers. We present also the list of the 2nd shell harmonics (SAXS reflections) allowed and prohibited in some of the non-conventional morphologies due to the weak segregation considerations and comparison of our results with the preceding SCFT treatment of the ABC copolymers by Matsen.     

Nanoscopic surface patterns of diblock copolymer thin films

The surface topography of thin diblock copolymer films is studied by atomic force microscopy (AFM). With AFM an island-to-ribbon transition is observed for symmetric polystyrene-b-poly (4-vinylpyridine) (PS-b-P4VP) on mica with increasing solution concentration. Our study also demonstrates how the formation of the pattern strongly depends on the copolymer composition based on the volume fraction. The substrate and solvent used both have great effects on the morphology of the thin films. Only by using highly polar substrate (mica), can we gain regular pattern. The reason why the regular islands cannot be obtained with symmetric PS-b-P4VP on graphite is also explained. On mica using nonselective and selective solvents, a rather regular pattern can be obtained. The difference is only in the solution concentration for forming regular patterns.     

Nonlinear competition between asters and stripes in filament-motor systems

A model for polar filaments interacting via molecular motor complexes is investigated which exhibits bifurcations to spatial patterns. It is shown that the homogeneous distribution of filaments, such as actin or microtubules, may become either unstable with respect to an orientational instability of a finite wave number or with respect to modulations of the filament density, where long-wavelength modes are amplified as well. Above threshold nonlinear interactions select either stripe patterns or periodic asters. The existence and stability ranges of each pattern close to threshold are predicted in terms of a weakly nonlinear perturbation analysis, which is confirmed by numerical simulations of the basic model equations. The two relevant parameters determining the bifurcation scenario of the model can be related to the concentrations of the active molecular motors and of the filaments, respectively, which both could be easily regulated by the cell.