Shear modulus of polydomain, mono-domain and non-mesomorphic side-chain elastomers: Influence of the nematic order

We investigate the behavior of the complex shear modulus of a series of elastomers including mono-domain and poly-domain liquid crystal samples, and a non-mesomorphic sample. We find that the dynamics of the glass transition are strongly modified by the nematic order. This result explains why the truly elastic response of liquid crystal elastomers can only be observed in the isotropic phase at very high temperatures and at very low frequencies. Between the elastic regime and the glassy state, the elastomers have a visco-elastic regime, which is characterized by a Rouse-like behavior for mono-domain and poly-domain samples, and by a Zimm-like behavior for the non-mesomorphic sample. We also show that the mono-domain sample exhibits marked anisotropy of the shear-modulus G ^′. This anisotropy, which is observed for the first time, is a function of frequency and is inverted between low and high frequencies, due to relaxation effects of the orientational order. Received 28 January 2000 and Received in final form 16 October 2000     

Simple Landau model of the smectic- A-isotropic phase transition

A simple Landau-type free energy function is presented to describe the smectic-A-isotropic phase transition. Varying the coupling between orientational and positional order parameters, a smectic-A-isotropic or a nematic-isotropic phase transition occurs. Within this model the smectic-A-isotropic phase transition is found to be always more strongly first order than the nematic-isotropic phase transition. The theoretical results are found to be in good agreement with all published experimental results. Received 27 June 2000     

Director configuration and dynamics of a nematic liquid crystal around a two-dimensional spherical particle: Numerical analysis using adaptive grids

We study numerically the director and orientational order parameter configurations in a nematic liquid crystal around a two-dimensional spherical particle on the basis of the tensor order parameter formalism. To properly account for the large length scale difference between the particle and the accompanying orientational defect, we devise an adaptive grid scheme in which the lattice spacing is automatically and locally adjusted in response to the spatial gradient of the orientational order parameter. This adaptive grid scheme is useful in studying dynamical as well as static orientational structures. We present a simulation result which shows how a hedgehog defect of topological charge -1 becomes unstable in two dimensions, and splits into a defect pair of topological charge -1/2, located symmetrically around the particle. Received 14 September 2000 and Received in final form 27 December 2000     

Quantum chemical construction of a reduced reaction Hamiltonian and T 1 -relaxation and pure T 2 -dephasing rates for the proton transfer in 3-chlorotropolone

Separating multidimensional problems into that of a relevant system which is coupled to a bath of harmonic oscillators is a common concept in condensed phase theory. Focusing on the specific problem of intramolecular proton transfer in an isolated tropolone derivative, we consider the reactive proton moving in the plane of the molecule as the system and the remaining substrate normal modes as the bath. An all-Cartesian system-plus-substrate Hamiltonian is constructed employing density functional theory. It is then used to determine the temperature-dependent effective reduced reaction Hamiltonian and the state-to-state dissipation rates induced via the system-substrate coupling up to the bi-quadratic order. The important substrate modes for the T₁-relaxation and the pure T₂-dephasing rates, which are either intra- or inter-well in nature, are identified numerically and analyzed physically with molecular details. Received 19 November 2001 and Received in final form 19 February 2002     

Electron phonon interactions and superconductivity in α ′ -TTF[Pd(dmit)2]2

A simple model is developed to understand superconductivity in α ^′ -TTF[Pd(dmit)₂]₂. We include electron-intra molecular and intermolecular phonon interactions as the mechanism of superconductivity. Intramolecular vibrations included are the eight symmetric A_g modes of the Pd(dmit)₂ molecule. Intermolecular vibrations included are the longitudinal acoustic and transverse acoustic (LA and TA) modes of the Pd(dmit)₂ column. All the electron-phonon coupling constants are calculated from first principles. We find that largest el-intramolecular vibration coupling is to the A_g mode with the highest frequency (1449 cm^-1). The el-intermolecular coupling to the LA mode is found to be larger than the total el-intramolecular couplings. We also find el-(TA)phonon coupling to be at least an order of magnitude smaller than el-(LA)phonon coupling. Estimate of superconducting transition temperature is comparable to experimental result. We also provide a detailed discussion, employing the results of recent numerical calculations on two-chain Hubbard model and the specific material parameters, on the relative importance of el-ph and Coulomb-origin mechanisms of superconductivity in α ^′ -TTF[Pd(dmit)₂]₂ and TTF[Ni(dmit) ₂ ] ₂ . Received 29 March 2001 and Received in final form 7 August 2001     

Orientation-dependent depletion interaction in rodlike colloid-polymer mixtures

Depletion interaction in a suspension of rodlike colloids with added non-adsorbing polymer coils is theoretically studied. We calculate an overlap volume of depletion zone between two rodlike colloids, based on the second virial approximation. We examine nematic-isotropic phase transition (NIT) and two-phase coexistence between an isotropic and a nematic phase at low polymer concentrations. We find that the depletion interaction is dependent on the orientational order parameter of rodlike colloids and leads to a decrease in the NIT concentration on the addition of polymer. The coexistence curves have a leaning-chimney shape and are shifted to lower rod concentrations on increasing the polymer concentration. Received 23 May 2001 and Received in final form 18 July 2001     

Coupling and dissociation in artificial molecules

We show that the spin-and-space unrestricted Hartree-Fock method, in conjunction with the companion step of the restoration of spin and space symmetries via Projection Techniques (when such symmetries are broken), is able to describe the full range of couplings in two-dimensional double quantum dots, from the strong-coupling regime exhibiting delocalized molecular orbitals to the weak-coupling and dissociation regimes associated with a Generalized Valence Bond combination of atomic-type orbitals localized on the individual dots. The weak-coupling regime is always accompanied by an antiferromagnetic ordering of the spins of the individual dots. The cases of dihydrogen (H₂, 2e) and dilithium (Li₂, 6e) quantum dot molecules are discussed in detail. Received 19 December 2000     

The timescale of spinodal dewetting at a polymer/polymer interface

We investigate the dynamics of spinodal dewetting in liquid-liquid polymer systems. Dewetting of poly(methyl-methacrylate) (PMMA) thin films on polystyrene (PS) “substrates” is followed in situ using neutron reflectivity. By following the development of roughness at the PS/PMMA interface and the PMMA surface we extract characteristic growth times for the dewetting process. These characteristic growth times are measured as a function of the molecular weight of the two polymers. By also carrying out experiments in the regime where the dynamics are independent of the PS molecular weight, we are able to use dewetting to probe the scaling of the PMMA thin film viscosity with temperature and molecular weight. We find that this scaling reflects bulk behaviour. However, absolute values are low compared to bulk viscosities, which we suggest may be due in part to slippage at the polymer/polymer interface. Received 25 June 2001 and Received in final form 5 December 2001     

Spatial reorientation of azobenzene side groups of a liquid crystalline polymer induced by linearly polarized light

The photoinduced 3D orientational structures in films of a liquid crystalline polyester, containing azobenzene side groups, are studied both experimentally and theoretically. By using the null ellipsometry and the UV/Vis absorption spectroscopy, the preferential in-plane alignment of the azobenzene fragments and in-plane reorientation under irradiation with linearly polarized UV light are established. The uniaxial and biaxial orientational order of the azobenzene chromophores are detected. The biaxiality is observed in the intermediate stages of irradiation, whereas the uniaxial structure is maintained in the photosaturated state of the photo-orientation process. The components of the order parameter tensor of the azobenzene fragments are estimated for the initial state and after different doses of irradiation. The proposed theory takes into account biaxiality of the induced structures. Numerical analysis of the master equations for the order parameter tensor is found to yield the results that are in good agreement with the experimental dependencies of the order parameter components on the illumination time. Received 23 April 2001 and Received in final form 1 August 2001     

Formation and decay of super-heavy systems

We investigate the formation and the decay of heavy systems which are above the fission barrier. By using a microscopic simulation of constrained molecular dynamics (CoMD) on Au + Au collision, we observe that composite states stay for a very long time before decaying by fission. Received: 13 December 2001 / Accepted: 19 March 2002     

Macroscopic oscillations between two weakly coupled Bose-Einstein condensates

We demonstrate, both from a theoretical and an experimental point of view, the possibility of realizing a weak coupling between two Bose-Einstein condensates trapped in different Zeeman states. The weak coupling drives macroscopic quantum oscillations between the condensate populations and the observed current-phase dynamics is described by generalized Josephson equations. In order to highlight the superfluid nature of the oscillations, we investigate the response of a ⁸⁷Rb non-condensate (thermal) gas in the same conditions, showing that the thermal oscillations damp more quickly than those of the condensate. Received 2 May 2002 / Received in final form 19 November 2002 Published online 6 March 2003 RID="a" ID="a"e-mail: smerzi@sissa.it     

Eigenstates of an operating quantum computer: hypersensitivity to static imperfections

We study the properties of eigenstates of an operating quantum computer which simulates the dynamical evolution in the regime of quantum chaos. Even if the quantum algorithm is polynomial in number of qubits n_q, it is shown that the ideal eigenstates become mixed and strongly modified by static imperfections above a certain threshold which drops exponentially with n_q. Above this threshold the quantum eigenstate entropy grows linearly with n_q but the computation remains reliable during a time scale which is polynomial in the imperfection strength and in n_q. Received 7 March 2002/ Received in final form 3 May 2002 Published online 19 July 2002     

Controlling wettability by light: illuminating the molecular mechanism

The functionalisation of a surface with an organic monolayer containing photoactive moieties such as the azobenzene chromophore opens an elegant route for controlling its wettability by light. In this paper we investigate the microscopic origin of the macroscopic change in wettability upon photo-induced cis-trans isomerization of a copolymeric diphenyl-diazene Langmuir-Blodgett monolayer. Polarised UV-Vis and FTIR spectroscopy have been used to monitor the orientational order of various functional groups, Atomic Force Microscopy and Imaging Ellipsometry is employed for the quantification of the surface roughness and morphology, contact angle and surface potential measurements are carried out for a characterisation of the polar ordering. The data analysis is further supported by semi-empirical and ab-initio calculations of the molecular dipole moments and the normal IR-modes of the fluorinated chromophore. The combination of all these techniques provides a detailed molecular picture. The data suggest that changes in the projection of the dipole moment onto the surface normal caused by isomerization of the azobenzene are responsible for the observed changes in the surface energy. This knowledge allowed us to predict guidelines for the synthesis of molecules in order to maximize the wetting contrast upon photo-irradiation. Received 5 September 2002 Published online: 16 April 2003 RID="a" ID="a"e-mail: hubert.motschmann@mpikg-golm.mpg.de     

Stability criterions of an oscillating tip-cantilever system in dynamic force microscopy

This work is a theoretical investigation of the stability of the non-linear behavior of an oscillating tip-cantilever system used in dynamic force microscopy. Stability criterions are derived that may help to a better understanding of the instabilities that may appear in the dynamic modes, Tapping and NC-AFM, when the tip is close to a surface. A variational principle allows to get the temporal dependence of the equations of motion of the oscillator as a function of the non-linear coupling term. These equations are the basis for the analysis of the stability. One find that the branch associated to frequencies larger than the resonance is always stable whereas the branch associated to frequencies smaller than the resonance exhibits two stable domains and one unstable. This feature allows to re-interpret the instabilities appearing in Tapping mode and may help to understand the reason why the NC-AFM mode is stable. Received 12 April 2001     

Statistical properties of eigenvalues for an operating quantum computer with static imperfections

We investigate the transition to quantum chaos, induced by static imperfections, for an operating quantum computer that simulates efficiently a dynamical quantum system, the sawtooth map. For the different dynamical regimes of the map, we discuss the quantum chaos border induced by static imperfections by analyzing the statistical properties of the quantum computer eigenvalues. For small imperfection strengths the level spacing statistics is close to the case of quasi-integrable systems while above the border it is described by the random matrix theory. We have found that the border drops exponentially with the number of qubits, both in the ergodic and quasi-integrable dynamical regimes of the map characterized by a complex phase space structure. On the contrary, the regime with integrable map dynamics remains more stable against static imperfections since in this case the border drops only algebraically with the number of qubits. Received 19 June 2002 / Received in final form 30 September 2002 Published online 17 Decembre 2002 RID="a" ID="a"e-mail: dima@irsamc.ups-tlse.fr RID="b" ID="b"UMR 5626 du CNRS     

Phonon density-of-states in the new superconductor MgB 2

We provide here experimental data on the phonon density-of-states of MgB₂ obtained by the inelastic neutron scattering technique. The measurements were performed for the natural boron-based magnesium diboride with use of a time-of-flight neutron spectrometer. Several phonon bands were observed in the phonon spectrum at energies of about 33, 55, 82 and 99 meV. We show that the cut-off energy of the density-of-states occurs at around 105 meV which is much higher than expected so far from heat-capacity data and partially explains the high T _c value observed for MgB₂. The characteristic phonon energies are indicative of an intermediate coupling regime in this compound. We conclude that a much needed neutron experiment aimed at the study of the isotopic effect in the phonon density-of-states of MgB₂ is conceivable. Received 19 March 2001     

On the theory of light scattering in molecular liquids

The theory of light scattering for a system of linear molecules with anisotropic polarizabilities is considered. As a starting point for our theory, we express the result of a scattering experiment in VV and VH symmetry as dynamic correlation functions of tensorial densities ρ _lm(q) with l = 0 and l = 2. l, m denote indices of spherical harmonics. To account for all observed hydrodynamic singularities, a generalization of the theory of Schilling and Scheidsteger [1] for these correlation functions is presented, which is capable to describe the light scattering experiments from the liquid regime to the glassy state. As a microscopic theory it fulfills all sum rules contrary to previous phenomenological theories. We emphasize the importance of the helicity index m for the microscopic theory by showing, that only the existence of m = 1 components lead to the well known Rytov dip in liquids and to the appearance of transversal sound waves in VH symmetry in the deeply supercooled liquid and the glass. Exact expressions for the phenomenological frequency dependent rotation translation coupling coefficients of previous theories are derived. Received 3 July 2000 and Received in final form 7 November 2000     

Observation of a re-entrant kinetic glass transition in a micellar system with temperature-dependent attractive interaction

We detect in a tri-block co-polymer micellar system an ergodic-to-nonergodic-to-ergodic transition, as a function of temperature, in a range of concentrations, by photon correlation measurements. The shear viscosity is also shown to jump two order of magnitude at these transition temperatures. Surprisingly, the structure factor as measured by small angle neutron scattering shows a marked narrowing at the structural arrest state. Rationalization of these results with the existence of an attractive branch in the phase diagram of an attractive colloid system predicted by mode coupling theory is made. Received 9 Aprile 2002     

X-ray scattering study of the phase transitions in crystalline fullerene-biphenyl C 60 [(C 6 H 5 ) 2 ]

The phase diagram of the newly synthesized mixed crystal C₆₀-biphenyl is investigated as a function of temperature by single-crystal X-ray scattering. Diffuse scattering investigations evidencing complex disorder and local order effects are presented. Two phase transitions leading to two different doublings of the high temperature unit cell are observed, at 212 K and 147 K. The first transition is attributed to the ordering of twisted biphenyls, which couples to the orientational ordering of the C₆₀ molecules as the temperature decreases. Full ordering of the C₆₀ molecules is achieved below 100 K only, in the low temperature phase. The rich phase diagram of C₆₀-biphenyl is due to the interplay between fullerene and biphenyl ordering phenomena. Received 31 August 2001 and Received in final form 4 December 2001     

Polaronic behavior in single- and many-electron Holstein model: A new perturbation approach

A new perturbation approach is developed for single- and many-electron Holstein model in one-, two-, and three-dimension. The results show that this approach has a good agreement with the Migdal theory in the adiabatic regime when the coupling is moderate (λ < 1), but with the Lang-Firsov theory in the antiadiabatic regime ( ω/W≫ 1). In the intermediate region, our approach can describe the transition from a large-polaron Fermi-liquid to the small-polaron, and this transition may be discontinuous in adiabatic regime, which means a phase transition appears in many-electron system. In single-electron case, we eliminate the abrupt transition using the degenerate perturbation theory, and the calculated ground state energy and effective mass are successfully compared with those of previous authors. Besides, the method has the advantage of requiring little computational effort. Received 27 December 2001 / Received in final form 8 April 2002 Published online 31 July 2002