Structure and diffusion in amorphous aluminum silicate: a molecular dynamics computer simulation

The amorphous aluminum silicate (Al2O3)2(SiO2) [AS2] is investigated by means of large scale molecular dynamics computer simulations. We consider fully equilibrated melts in the temperature range 6100 K> or =T> or =2300 K as well as glass configurations that were obtained from cooling runs from T=2300 to 300 K with a cooling rate of about 10(12) K/s. Already at temperatures as high as 4000 K, most of the Al and Si atoms are fourfold coordinated by oxygen atoms. Thus, the structure of AS2 is that of a disordered tetrahedral network. The packing of AlO4 tetrahedra is very different from that of SiO4 tetrahedra in that Al is involved with a relatively high probability in small-membered rings and in triclusters in which an O atom is surrounded by four cations. We find as typical configurations two-membered rings with two Al atoms in which the shared O atoms form a tricluster. On larger length scales, the system shows a microphase separation in which the Al-rich network structure percolates through the SiO2 network. The latter structure gives rise to a prepeak in the static structure factor at a wave number q=0.5 A(-1). A comparison of experimental x-ray data with the results from the simulation shows good agreement for the structure function. The diffusion dynamics in AS2 is found to be much faster than in SiO2. We show that the self-diffusion constants for O and Al are very similar and that they are by a factor of 2-3 larger than the one for Si.     

Stability of smectic phases in the Gay-Berne model

We present a detailed computer simulation study of the phase behavior of the Gay-Berne liquid crystal model with molecular anisotropy parameter kappa=4.4. According to previous investigations: (i) this model exhibits isotropic (I), smectic-A (Sm-A), and smectic-B (Sm-B) phases at low pressures, with an additional nematic (N) phase between the I and Sm-A phases at sufficiently high pressures; (ii) the range of stability of the Sm-A phase turns out to be essentially constant when varying the pressure, whereas other investigations seem to suggest a pressure-dependent Sm-A range; and (iii) the range of stability of the Sm-B phase remains unknown, as its stability with respect to the crystal phase has not been previously considered. The results reported here do show that the Sm-A phase is stable over a limited pressure range, and so it does not extend to arbitrarily low or high pressures. This is in keeping with previous investigations of the effect of molecular elongation on the phase behavior of Gay-Berne models. A detailed study of the melting transition at various pressures shows that the low-temperature crystalline phase melts into an isotropic liquid at very low pressures, and into a nematic liquid at very high pressures. At intermediate pressures, the crystal melts into a Sm-A liquid and no intermediate Sm-B phase is observed. On the basis of this and previous investigations, the reported Sm-B phase for Gay-Berne models appears to be a molecular solid rather than a smectic liquid phase.     

Computer simulation studies of anisotropic systems. XIX. Mesophases formed by the Gay-Berne model mesogen

We report the results of a molecular dynamics computer simulation of particles interacting via the Gay-Berne potential with parameters selected to approximate those of mesogenic molecules. The system was found to form a variety of mesophases as the temperature was lowered. We have characterized these phases with the aid of computer graphics techniques to visualize the molecular organization within configurations taken from the production stage of the simulations. The phases have been identified, on the basis of such images, as isotropic, nematic, smectic A, smectic B and crystal.     

Molecular dynamics simulation study on the phase behavior of the Gay-Berne model with a terminal dipole and a flexible tail

To study the effect of the alkyl tail and the terminal dipole on the stability of the liquid crystalline phase of mesogens, we have carried out molecular dynamics simulations for 1CB(4-methyl-4'-cyanobiphenyl) and 5CB(4-n-pentyl-4'-cyanobiphenyl) by using a coarse-grained model. In the coarse-grained model, a 5CB molecule is divided into the rigid part of 1CB moiety, which is represented by an ellipsoid, and the remaining flexible part which is represented by a chain of united atoms. The nonbonded potential between coarse-grained segments is represented by the generalized Gay-Berne (GB) potential and the potential parameters are determined by directly comparing the GB potential with the atomistic potentials averaged over the rotation of the mesogen around its axis. In addition, a dipole moment is placed at one end of the ellipsoid opposite to the flexible tail. The ordered state obtained in the polar 5CB model was assigned as the nematic phase, and the experimental static and dynamical properties were reproduced well by using this coarse-grained model. Both the dipole-dipole interactions and the thermal fluctuation of the flexible tail increase the positional disorder in the director direction, and stabilize the nematic phase. Thus, the nematic phase in the polar 5CB is induced by a cooperative effect of the flexible tail and the terminal dipole. It is noted that a local bilayer structure with head-to-head association is formed in the nematic phase, as experimentally observed by x-ray diffraction measurements.     

Structure and dynamics of a fluid phase bilayer on a solid support as observed by a molecular dynamics computer simulation

Simulations of a 1-palmitoyl-2-oleoyl- sn-glycero-3-phosphocholine lipid bilayer interacting with a solid surface of hydroxylated nanoporous amorphous silica have been carried out over a range of lipid-solid substrate distances. The porous solid surface allowed the water layer to dynamically adjust its thickness, maintaining equal pressures above and below the membrane bilayer. Qualitative estimates of the force between the surfaces leads to an estimated lipid-silicon distance in very good agreement with the results of neutron scattering experiments. Detailed analysis of the simulation at the separation suggested by experiment shows that for this type of solid support the water layer between surfaces is very narrow, consisting only of bound waters hydrating the lipid head groups and hydrophilic silica surface. The reduced hydration, however, has only minor effects on the head group hydration, the orientation of water molecules at the interface, and the membrane dipole potential. Whereas these structural properties were not sensitive to the presence of the solid substrate, the calculated diffusion coefficient for translation of the lipid molecules was altered significantly by the silica surface.     

A polycatenar mesogen with a perfluorinated moiety showing continuous phase transformation between a smectic A phase and a structured,fluid, optically isotropic phase

A polycatenar mesogen consisting of a four aromatic ring system with three long alkoxy chains and a bulky perfluorinated substituent has been synthesized and found to show the polymorphism of a cubic phase, a columnar phase and a smectic A phase, including a structured, fluid, optically isotropic phase with the phase transformation between the smectic A phase and the isotropic phase occurring continuously.     

Decoupling effects in computer simulation of liquid-state molecular dynamics

Decoupling effects in liquid-state molecular dynamics are unambiguously proven by computer simulations. These can be discribed as the weakening of the dissipative interaction between the system if interest (e.g. molecular angular valocity) and its thermal bath caused by an intense external field of force. The new phenomenon may be used to confirm or challenge the validity of simple models of the liquids state of molecular matter and provide information on the microscopic time scale.     

A molecular model for the smectic B phase. The stabilized molecular rotor

Transition temperatures and smectic B mesophase ranges are examined for a number of homologous series, and some general rules are proposed that relate the smectic B phase behaviour to molecular structure. A mechanical model is developed for the crystal and hexatic smectic B phases, based on the dynamics of rigid or elastic rotors, which suggests two possible types of behaviour. It is found that such predicted behaviour is observed for particular series, but in general the smectic B phase characteristics of homologous series may be between the limits established for the model.     

Understanding diffusion in confined systems: methane in a ZK4 molecular sieve. A molecular dynamics simulation study

The equilibrium probability distribution of N methane molecules adsorbed in the interior of n alpha cages of the ZK4 zeolite, the all-silica analogue of zeolite A, is modeled by a modified hypergeometric distribution where the effects of mutual exclusion between particles are extracted from long molecular dynamics simulations. The trajectories are then analyzed in terms of time-correlation functions for the fluctuations in the occupation number of the alpha cages. The analysis digs out the correlations induced by the spatial distribution of the adsorbed molecules coupled with a migration mechanism where a molecule can pass from one alpha cage to another, one-by-one. These correlations lead to cooperative motion, which manifests itself as a nonexponential decay of the correlators. Our results suggest ways of developing improved lattice approaches that may be useful for studying diffusion in much larger systems and for a much longer observation time.     

Electrolysis of water in the diffusion layer: first-principles molecular dynamics simulation

With Car-Parrinello molecular dynamics simulations the elementary reaction steps of the electrolysis of bulk water are investigated. To simulate the reactions occurring near the anode and near the cathode, electrons are removed or added, respectively. The study focuses on the reactions in pure water. Effects depending on a particular electrode surface or a particular electrolyte are ignored. Under anodic conditions, the reaction continues till molecular oxygen is formed, under cathodic conditions the formation of molecular hydrogen is observed. In addition the formation of hydrogen peroxide is observed as an intermediate of the anodic reaction. The simulations demonstrate that the electrochemistry of oxygen formation without direct electrode contact can be explained by radical reactions in a solvent. These reactions may involve the intermediate formation of ions. The hydrogen formation is governed by rapid proton transfers between water molecules.     

A re-entrant smectic C phase in a sequence smectic C-oblique columnar-smectic C-nematic

A new six-ring double-swallow-tailed compound is presented which exhibits a re-entrant smectic C phase in the sequence smectic C-oblique columnar-smectic C-nematic. This unusual sequence detected by observation of the optical textures and by X-ray investigations is also confirmed by the phase diagrams with homologous compounds.     

Molecular dynamics of a short-range ordered smectic phase nanoconfined in porous silicon

4-n-octyl-4-cyanobiphenyl has been recently shown to display an unusual sequence of phases when confined into porous silicon (PSi). The gradual increase of oriented short-range smectic (SRS) correlations in place of a phase transition has been interpreted as a consequence of the anisotropic quenched disorder induced by confinement in PSi. Combining two quasielastic neutron scattering experiments with complementary energy resolutions, the authors present the first investigation of the individual molecular dynamics of this system. A large reduction of the molecular dynamics is observed in the confined liquid phase, as a direct consequence of the boundary conditions imposed by the confinement. Temperature fixed window scans reveal a continuous glasslike reduction of the molecular dynamics of the confined liquid and SRS phases on cooling down to 250 K, where a solidlike behavior is finally reached by a two-step crystallization process.     

Molecular dynamics simulations of discotic liquid crystals using a hybrid Gay-Berne Luckhurst-Romano potential

We report the results of the computer simulation of a collection of particles interacting via an anisotropic potential proposed by Luckhurst and Romano and modified by scaling with part of the anisotropic well depth formalism employed by Gay-Berne. Using the molecular dynamics technique for 256 particles in the NVE ensemble, the system is shown to exhibit a variety of mesophases, as the temperature is lowered, and these are provisionally identified as isotropic, discotic nematic, a highly ordered fluid phase with some columnar features and a crystal.     

Direct effect of nanoparticles on the thermal conductivity of CuO-water nanofluid in a phase transition phenomenon using molecular dynamics simulation

Journal of Thermal Analysis and Calorimetry - The thermal behavior of CuO-water nanofluid is examined on an aluminum surface. The dimensions of simulation boxes are...     

Solvation shell dynamics studied by molecular dynamics simulation in relation to the translational and rotational dynamics of supercritical water and benzene

The solvation shell dynamics of supercritical water is analyzed by molecular dynamics simulation with emphasis on its relationship to the translational and rotational dynamics. The relaxation times of the solvation number (tau S), the velocity autocorrelation function (tau D), the angular momentum correlation function (tau J), and the second-order reorientational correlation function (tau 2R) are studied at a supercritical temperature of 400 degrees C over a wide density region of 0.01-1.5 g cm(-3). The relaxation times are decomposed into those conditioned by the solvation number n, and the effect of the short-ranged structure is examined in terms of its probability Pn of occurrence. In the low to medium-density range of 0.01-0.4 g cm(-3), the time scales of water dynamics are in the following sequence: tau D>tau S approximately or > tau J approximately or > tau 2R. This means that the rotation in supercritical water is of the "in-shell" type while the translational diffusion is not. The comparison to supercritical benzene is also performed and the effect of hydrogen bonding is examined. The water diffusion is not of the in-shell type up to the ambient density of 1.0 g cm(-3), which corresponds to the absence of the transition from the collision to the Brownian picture, whereas such transition is present in the case of benzene. The absence of the transition in water comes from the fast reorganization of the hydrogen bonds and the enhanced mobility of the solvation shell in supercritical conditions.     

Molecular dynamics simulation study on the transient response of solvation structure during the translational diffusion of solute

The transient response function of the density profile of the solvent around a solute during the translational diffusion of the solute is formulated based on the generalized Langevin formalism. The resultant theory is applied to both neat Lennard-Jones fluids and cations in liquid water, and the response functions are obtained from the analysis of the molecular dynamics simulations. In the case of the self-diffusion of Lennard-Jones fluids, the responses of the solvation structures are in harmony with conventional pictures based on the mode-coupling theory, that is, the binary collision in the low-density fluids, the backflow effect from medium to high density fluids, and the backscatter effect in the liquids near the triple point. In the case of cations in water, the qualitative behavior is strongly dependent on the size of cations. The pictures similar to simple dense liquids are obtained for the large ion and the neutral molecule, while the solvent waters within the first solvation shell of small ions show an oscillatory response in the short-time region. In particular, the oscillation is remarkably underdumped for lithium ion. The origin of the oscillation is discussed in relation to the theoretical treatment of the translational diffusion of ions in water.     

Relation between amorphous structure of polymers and penetrant diffusion: A molecular dynamics simulation

Molecular dynamics simulation has been performed for studying the relation between amorphous structure of polymers and penetrant diffusion. The self-diffusion coefficients of O₂ and He in various polymer models, which differ from each other in view of the amorphous structure, were calculated above their glass transition temperatures. The amorphous structure was characterized by considering the percolation of the unoccupied volume. A good correlation was found between the self-diffusion coefficients and the number of clusters in the unoccupied volume at the critical point of the percolation. Based on the simulated cluster size distribution at the critical point, we defined a parameter into which effects of both the amorphous structure and the penetrant size are well incorporated. It was confirmed that the penetrant diffusion is intimately associated with the amorphous structure of polymers.