Polymers with both soluble and insoluble blocks typically self-assemble into micelles, aggregates of a finite number of polymers where the soluble blocks shield the insoluble ones from contact with the solvent. Upon increasing concentration, these micelles often form gels that exhibit crystalline order in many systems. In this paper, we present a study of both the dynamics and the equilibrium properties of micellar crystals of triblock polymers using molecular dynamics simulations. Our results show that equilibration of single micelle degrees of freedom and crystal formation occurs by polymer transfer between micelles, a process that is described by transition state theory. Near the disorder (or melting) transition, bcc lattices are favored for all triblocks studied. Lattices with fcc ordering are also found, but only at lower kinetic temperatures and for triblocks with short hydrophilic blocks. Our results lead to a number of theoretical considerations and suggest a range of implications to experimental systems with a particular emphasis on Pluronic polymers.
We study the freezing kinetics of colloidal polycrystals made of micelles of Pluronic F108, a thermosensitive copolymer, to which a small amount of silica nanoparticles of size comparable to that of the micelles are added. We use rheology and calorimetry to measure Tc, the crystallization temperature, and find that Tc increases with the heating rate \dot{T} used to crystallize the sample. To rationalize our results, we first use viscosity measurements to establish a linear mapping between temperature T and the effective volume fraction, ϕ, of the micelles, treated as hard spheres. Next, we rep…
The dynamics of hydrogen bonds among water molecules themselves and with the polar head groups (PHG) at a micellar surface have been investigated by long molecular dynamics simulations. The lifetime of the hydrogen bond between a PHG and a water molecule is found to be much longer than that between any two water molecules, and is likely to be a general feature of hydrophilic surfaces of organized assemblies. Analyses of individual water trajectories suggest that water molecules can remain bound to the micellar surface for more than a hundred picosecond. The activation energy for such a transit…
We investigate by scattering techniques the structure of water-based soft composite materials comprising a crystal made of Pluronic block-copolymer micelles arranged in a face-centered cubic lattice and a small amount (at most 2% by volume) of silica nanoparticles, of size comparable to that of the micelles. The copolymer is thermosensitive: it is hydrophilic and fully dissolved in water at low temperature (T ~ 0°C), and self-assembles into micelles at room temperature, where the block-copolymer is amphiphilic. We use contrast matching small-angle neuron scattering experiments to probe indepen…
We propose a physical mechanism to explain the crystal symmetries found in macromolecular and supramolecular micellar materials. We argue that the packing entropy of the hard micellar cores is frustrated by the entropic interaction of their brush-like coronas. The latter interaction is treated as a surface effect between neighboring Voronoi cells. The observed crystal structures correspond to the Kelvin and Weaire-Phelan minimal foams. We show that these structures are stable for reasonable areal entropy densities.
Linking molecular timescales to linear viscoelastic response in dilute and semidilute unentangled wormlike micelle solutions
IITB-Monash Research Academy（IITB-蒙纳士研究学院）；Department of Chemical Engineering, Indian Institute of Technology Bombay（印度理工学院孟买分校化学工程系）；Department of Chemical and Biological Engineering, Monash University（蒙纳士大学化学与生物工程系）；School of Chemistry, Monash University（蒙纳士大学化学学院）
A mean-field kinetic model suggests that the relaxation dynamics of wormlike micellar networks is a long and complex process due to the problem of reducing the number of free end-caps (or dangling ends) while also reaching an equilibrium level of branching after an earlier overgrowth. The model is validated against mesoscopic molecular dynamics simulations and is based on kinetic equations accounting for scission and synthesis processes of blobs of surfactants. A long relaxation time scale is reached both with thermal quenches and small perturbations of the system. The scaling of this relaxati…
Many ionic surfactants with wide applications in personal-care and house-hold detergency show limited water solubility at lower temperatures (Krafft point). This drawback can be overcome by using mixed solutions, where the ionic surfactant is incorporated in mixed micelles with another surfactant, which is soluble at lower temperatures. The solubility and electrolytic conductivity for a binary surfactant mixture of anionic methyl ester sulfonates (MES) with nonionic alkyl polyglucoside and alkyl polyoxyethylene ether at 5 deg C during long-term storage were measured. Phase diagrams were establ…
In order to understand the nature and dynamics of interfacial water molecules on the surface of complex systems, large scale molecular dynamics simulations of an aqueous micelle of cesium perfluorooctanoate surfactant molecules have been carried out. The lifetime and the intermolecular vibrational frequencies of the hydrogen bonds that the water molecules form with the polar headgroups of the surfactants, are calculated. Our earlier classification of the interfacial water molecules, based on structural and energetic considerations, into bound and free type is further validated by their dynamic…
A nonequilibrium molecular dynamics computer simulation on microsegregated solutions of symmetrical diblock copolymers is reported. As the polymer concentration increases, the system undergoes phase transitions in the following order: body centered cubic (BCC) micelles, hexagonal (HEX) cylinders, gyroid (GYR) bicontinuous networks, and lamellae (L), which are the same morphologies that have been reported for block copolymer melts. Structural classification is based on the patterns of the anisotropic static structure factor and characteristic 3-dimensional images. The systems in the BCC micella…
We present a simple one-dimensional model with molecular interactions favouring the formation of clusters with a defined optimal size. Increasing the density, at low temperature, the system goes from a nearly-ideal gas of independent molecules to a system with most of the molecules in optimal clusters, in a way that resembles the formation of micelles in a dilution of amphiphilic molecules, at the critical micellar concentration. Our model is simple enough to have an exact solution, but it contains some basic features of more realistic descriptions of amphiphilic systems: molecular excluded vo…
Hypotheses: The aggregation number and length of spherocylindrical (rodlike, wormlike) micelles in solutions of an ionic surfactant and salt can be predicted knowing the molecular parameters and the input concentrations of the species. This can be achieved by upgrading the quantitative molecular thermodynamic model from the previous parts of this series with an expression for the electrostatic component of micelle scission energy that is the excess free energy of the spherical endcaps with respect to the cylindrical part of the micelle. Theory: The thermodynamics of micellization is extended t…
The influence of the molecular structure of the nematic liquid crystal (NLC) on the photoalignment process at the NLC -- polymer interface has been investigated experimentally. NLCs having exclusively phenyl-, or cyclohexane rings in the rigid core, as well as NLCs containing both phenyl and cyclohexane groups have been considered. Substantial differences have been found in the photoalignment process depending on the molecular structure of the NLC, supporting the assumption that the polymer -- NLC interface should be regarded as a coupled system, where the two components mutually influence eac…
Dense packing of particles has provided important models to study the structure of matter in various systems such as liquid, glassy and crystalline phase, etc. The simplest sphere packing models are able to represent and capture salient properties of the building blocks for covalent, metallic and ionic crystals; it however becomes insufficient to reflect the broken symmetry of the commonly anisotropic molecules in complex molecular crystals. Here we develop spheroid models with the minimal degree of anisotropy, which serve as a simple geometrical representation for a rich spectrum of molecules…
We propose a simple and reliable method to measure the liquid crystal surface anchoring strength by molecular simulation. The method is based on the measurement of the long-range fluctuation modes of the director in confined geometry. As an example, molecular simulations of a liquid crystal in slab geometry between parallel walls with homeotropic anchoring have been carried out using the Monte Carlo technique. By studying different slab thicknesses, we are able to calculate separately the position of the elastic boundary condition, and the extrapolation length.
Molecular process of crystallization from an oriented amorphous state was reproduced by molecular dynamics simulation for a realistic polyethylene model. Initial oriented amorphous state was obtained by uniaxial drawing an isotropic glassy state at 100 K. By the temperature jump from 100 K to 330 K, there occurred the crystallization into the fiber structure, during the process of which we observed the developments of various order parameters. The real space image and its Fourier transform revealed that a hexagonally ordered domain was initially formed, and then highly ordered crystalline stat…
We analize two anisotropic atom-atom models used to describe the crystalline alpha,beta and gamma phases of S8 crystals, the most stable compound of elemental sulfur in solid phases, at ambient pressure and T<=400 K. The calculations are performed via a series of classical molecular dynamics (MD) simulations, with flexible molecular models and using a constant pressure-constant temperature algorithm for the numerical simulations. All intramolecular modes that mix with lattice modes, and are therefore relevant on the onset of structural phase transitions, are taken into account. Comparisons wit…
The mobility of polymer chains in perfect polyethylene (PE) crystal was calculated as a function of temperature and chain length through Molecular dynamics (MD) in united atom approximation. The results demonstrate that the chain mobility drastically increases in the vicinity of the phase transition from the orthorhombic to quasi-hexagonal phase. In the quasi-hexagonal phase, the chain mobility is almost independent on temperature and inversely proportional to the chain length.
'Soft' patchy surfactant micelles have become an additional building tool in self-assembling systems. The triblock copolymer, Pluronic F108, forms spherical micelles in aqueous solutions upon heating leading to a simple phase diagram with a micellar crystalline solid at higher temperatures and concentrations. Here we report the strong influence of end-functionalising the chain ends either with an azide or azide-DNA complex on the systems' phase behaviour. We find that the azide(N3)- functionalisation renders the chain ends weakly hydrophobic at lower temperatures, causing them to self-assemble…
We study colloidal ordering and disordering on two-dimensional periodic substrates where the number of colloids per substrate minima is two or three. The colloids form dimer or trimer states with orientational ordering, referred to as colloidal molecular crystals. At a fixed temperature such that, in the absence of a substrate, the colloids are in a triangular floating solid state, upon increasing the substrate strength we find a transition to an ordered colloidal molecular crystal state, followed by a transition to a disordered state where the colloids still form dimers or trimers but the ori…
We present the first molecular dynamics study to probe the mechanisms of anomalous diffusion in cationic surfactant micelles in the presence of explicit salt and solvent-mediated interactions. Simulations show that when the counter ion density increases, saddle-shaped interfaces manifest leading to the formation of branched structures. In experiments, branched structures exhibit lower viscosity as compared to linear and wormlike micelles, presumably due to stress relaxation arising from the sliding motion of branches along the main chain. Our simulations provide conclusive evidence and a mecha…
Molecular simulations of a nematic liquid crystal confined in cylinder geometry with homeotropic anchoring have been carried out. The core structure of a disclination line defect of strength +1 has been examined, and comparison made with various theoretical treatments, which are presented in a unified way. It is found that excellent fits to the cylindrically-symmetrized order tensor profiles may be obtained with appropriate parameter choices; notwithstanding this, on the timescales of the simulation, the cylindrical symmetry of the core is broken and two defects of strength +1/2 may be resolve…
We develop a theory of Smectic A - Smectic C phase transition with anomalously weak smectic layer contraction. We construct a phenomenological description of this transition by generalizing the Chen-Lubensky model. Using a mean-field molecular model, we demonstrate that a relatively simple interaction potential suffices to describe the transition. The theoretical results are in excellent agreement with experimental data.
Using numerical simulations we show that a variety of novel colloidal crystalline states and multi-step melting phenomena occur on square and triangular two-dimensional periodic substrates. At half-integer fillings different kinds of frustration effects can be realized. A two-step melting transition can occur in which individual colloidal molecules initially rotate, destroying the overall orientational order, followed by the onset of interwell colloidal hopping, in good agreement with recent experiments.
Two dimensional suspensions of spherical colloids subject to periodic external fields exhibit a rich variety of molecular crystalline phases. We study in simulations the ground state configurations of dimeric and trimeric systems, that are realized on square and triangular lattices, when either two or three macroions are trapped in each external potential minimum. Bipartite orders of the checkerboard or stripe types are reported together with more complex quadripartite orderings, and the shortcomings of envisioning the colloids gathered in a single potential minimum as a composite rigid object…
Two-dimensional molecular crystals have been beyond the reach of systematic investigation because of the lack or instability of their well-defined forms. Here, we demonstrate drastically enhanced photostability and Davydov splitting in single and few-layer tetracene (Tc) crystals sandwiched between inorganic 2D crystals of graphene or hexagonal BN. Molecular orientation and long-range order mapped with polarized wide-field photoluminescence imaging and optical second-harmonic generation revealed high crystallinity of the 2D Tc and its distinctive orientational registry with the 2D inorganic cr…
We use first-principles computational methods to examine hole trapping in organic molecular crystals. We present a computational scheme based on the tuning of the fraction of exact exchange in hybrid density functional theory to eliminate the many-electron self-interaction error. With small organic molecules, we show that this scheme gives accurate descriptions of ionization and dimer dissociation. We demonstrate that the excess hole in perfect molecular crystals form self-trapped molecular polarons. The predicted absolute ionization potentials of both localized and delocalized holes are consi…
We study the driving of colloidal molecular crystals over periodic substrates such as those created with optical traps. The n-merization that occurs in the colloidal molecular crystal states produces a remarkably rich variety of distinct dynamical behaviors, including polarization effects within the pinned phase and the formation of both ordered and disordered sliding phases. Using computer simulations, we map the dynamic phase diagrams as a function of substrate strength for dimers and trimers on a triangular substrate, and correlate features on the phase diagram with transport signatures.
Free energy calculations of two crystalline phases of the molecular compound S8 were performed via molecular dynamics simulations of these crystals. The elemental sulphur S8 molecule model used in our MD calculations consists of a semi-flexible closed chain, with fixed bond lengths and intra-molecular potentials for its bending and torsional angles. The intermolecular potential is of the atom-atom Lennard-Jones type. Two free energy calculation methods were implemented: the accurate thermodynamic integration method proposed by Frenkel and Ladd and an estimation that takes into account the cont…
We show in simulations that a rich variety of novel orderings such as pinwheel and star states can be realized for colloidal molecular crystal mixtures at rational ratios of the number of colloids to the number of minima from an underlying periodic substrate. These states can have multi-step melting transitions and also show coexistence in which one species disorders while the other species remains orientationally disordered. For other mixtures, only partially ordered or frustrated states form.
The crystallization of a metastable melt is one of the most important non equilibrium phenomena in condensed matter physics, and hard sphere colloidal model systems have been used for several decades to investigate this process by experimental observation and computer simulation. Nevertheless, there is still an unexplained discrepancy between simulation data and experimental nucleation rate densities. In this paper we examine the nucleation process in hard spheres using molecular dynamics and Monte Carlo simulation. We show that the crystallization process is mediated by precursors of low orie…
Molecular packing, crystallinity, and texture of semiconducting polymers are often critical to performance. Although frame-works exist to quantify the ordering, interpretations are often just qualitative, resulting in imprecise and liberal use of terminology. Here, we reemphasize the continuity of the degree of molecular ordering and advocate that a more nuanced and consistent terminology is used with regards to crystallinity, semicyrstallinity, paracrystallinity, crystallite/aggregate, and related characteristics. We are motivated in part by our own imprecise and inconsistent use of terminolo…
Calculations of frequency spectra for organic molecular crystals taking various defects in their structure into account are carried out. It is shown how the presence of the vacancies, orientation disorder, and surface presence affects spectra. It was found, that each defect has the characteristic set of lines in the spectra.
We report on an infrared spectroscopy study of mobile holes in the accumulation layer of organic field-effect transistors based on rubrene single crystals. Our data indicate that both transport and infrared properties of these transistors at room temperature are governed by light quasiparticles in molecular orbital bands with the effective masses m* comparable to free electron mass. Furthermore, the m* values inferred from our experiments are in agreement with those determined from band structure calculations. These findings reveal no evidence for prominent polaronic effects, which is at varia…
Using numerical simulations, we investigate vortex configurations and pinning in superconductors with honeycomb and kagome pinning arrays. We find that a variety of novel vortex crystal states can be stabilized at integer and fractional matching field densities. The honeycomb and kagome pinning arrays produce considerably more pronounced commensuration peaks in the critical depinning force than triangular pinning arrays, and also cause additional peaks at noninteger matching fields where a portion of the vortices are located in the large interstitial regions of the pinning lattices. For the ho…
We investigate the defect structures forming around two nanoparticles in a Gay-Berne nematic liquid crystal using molecular simulations. For small separations, disclinations entangle both particles forming the figure of eight, the figure of omega and the figure of theta. These defect structures are similar in shape and occur with a comparable frequency to micron-sized particles studied in experiments. The simulations reveal fast transitions from one defect structure to another suggesting that particles of nanometre size cannot be bound together effectively. We identify the 'three-ring' structu…
We present a statistical mechanics approximation scheme for the explicit treatment of spacer-mediated configurational correlations among the mesogenic units that form a dimer molecule. The approximation is applied to the description of the nematic phase of linear uniaxial dimers interacting via a standard molecular pair-potential. Transition temperatures, order parameters and pair correlation averages are calculated for different spacer lengths. The results readily reproduce the experimentally observed trends of phase transition thermodynamics and of dipolar correlations deduced from dielectri…
We report a characterization of the relative stability and structural behavior of various micellar crystals of an athermal model of AB-diblock copolymers in solution. We adopt a previously devel- oped coarse-graining representation of the chains which maps each copolymer on a soft dumbbell. Thanks to this strong reduction of degrees of freedom, we are able to investigate large aggregated systems, and for a specific length ratio of the blocks f = MA/(MA + MB) = 0.6, to locate the order-disorder transition of the system of micelles. Above the transition, mechanical and thermal properties are fou…
Dependence of frequency spectra of the lattice oscillations of organic nano-crystals on temperature is studied at presence of vacancies in structure. In a frequency spectrum a number of additional lines monotonously changing with temperature is observed. Also, the spectrum of the surface oscillations is calculated at temperature change. At the same time, the low-frequency line has non-linear behavior with temperature change.
We explore the phase behavior and structure of orthogonal smectic liquid crystals consisting of bent-core molecules (BCMs) by means of Monte Carlo molecular simulations. A simple athermal molecular model is introduced that describes the basic features of the BCMs. Phase transitions between uniaxial and biaxial (antiferroelectric) orthogonal smectics are obtained. The results indicate the presence of local in-plane polar correlations in the uniaxial smectic phase. The macroscopic uniaxial-biaxial transformation is rationalized in terms of local polar correlations giving rise to polar domains. T…
We demonstrate orientation-sensitive multimodal nonlinear optical polarizing microscopy capable of probing orientational, polar, and biaxial features of mesomorphic ordering in soft matter. This technique achieves simultaneous imaging in broadband coherent anti-Stokes Raman scattering, multi-photon excitation fluorescence, and multi-harmonic generation polarizing microscopy modes and is based on the use of a single femtosecond laser and a photonic crystal fiber as sources of the probing light. We show the viability of this technique for mapping of three dimensional patterns of molecular orient…
