We show that to account for the full spectrum of surface fluctuations from low scattering vector qd << 1 (classical capillary wave theory) to high qd > 1 (bulk-like fluctuations), one must take account of the interface's bending rigidity at intermediate scattering vector qd = 1, where d is the molecular diameter. A molecular model is presented to describe the bending correction to the capillary wave model for short-ranged and long-ranged interactions between molecules. We find that the bending rigidity is negative when the Gibbs equimolar surface is used to define the location of the fluctuating interface and that on approach to the critical point it vanishes proportionally to the interfacial tension. Both features are in agreement with Monte Carlo simulations of a phase-separated colloid-polymer system.
We derive and analyze the dynamic equations for polar liquid crystals in two spatial dimensions in the framework of classical dynamical density functional theory (DDFT). Translational density variations, polarization, and quadrupolar order are used as order-parameter fields. The results are critically compared with those obtained using the macroscopic approach of time-dependent Ginzburg-Landau (GL) equations for the analogous order-parameter fields. We demonstrate that for both the microscopic DDFT and the macroscopic GL approach the resulting dissipative dynamics can be derived from a dissipa…
We propose a very simple but 'realistic' model of amphiphilic bilayers,simple enough to be able to include a large number of molecules in the sample, but nevertheless detailed enough to include molecular charge distributions, flexible amphiphilic molecules and a reliable model of water. All these parameters are essential in a nanoscopic scale study of intermolecular and long range electrostatic interactions. We also propose a novel, simple and more accurate macroscopic electrostatic field for model bilayers. This model goes beyond the total dipole moment of the sample, which on a time average …
Chiral smectic liquid crystals exhibit a series of phases, including ferroelectric, antiferroelectric and ferrielectric commensurate structures as well as an incommensurate SmCalpha phase. We carried out an extension of the phenomenological model, recently presented by M. B. Hamaneh and P. L. Taylor, based upon the distorted clock model.
Two-dimensional polar liquid crystals have been discovered recently in monolayers of anisotropic molecules. Here, we provide a systematic theoretical description of liquid-crystalline phases for polar particles in two spatial dimensions. Starting from microscopic density functional theory, we derive a phase-field-crystal expression for the free-energy density which involves three local order-parameter fields, namely the translational density, the polarization, and the nematic order parameter. Various coupling terms between the order-parameter fields are obtained which are in line with macrosco…
Molecular chirality leads to a wonderful variety of equilibrium structures, from the simple cholesteric phase to the twist-grain-boundary phases, and it is responsible for interesting and technologically important materials like ferroelectric liquid crystals. This paper will review some recent advances in our understanding of the connection between the chiral geometry of individual molecules and the important phenomenological parameters that determine macroscopic chiral structure. It will then consider chiral structure in columnar systems and propose a new equilibrium phase consisting of a reg…
We investigate the molecular origin of shear-thinning in melts of flexible, semiflexible and rigid oligomers with coarse-grained simulations of a sheared melt. Alignment, stretching and tumbling modes or suppression of the latter all contribute to understanding how macroscopic flow properties emerge from the molecular level. By performing simulations of single chains in a shear flow, we identify which of these phenomena are of collective nature and arise through interchain interactions and which are already present in dilute systems. Building upon these microscopic simulations we identify by m…
We study the transport and the relaxation properties of a molecular supercooled liquid by molecular-dynamics numerical simulations. The focus is on the translational motion. Jump motion is detected. At lower temperature the Stokes-Einstein law breaks down.
The rotational dynamics of a supercooled molecular liquid is investigated by a molecular-dynamics numerical study. We detect rotational jumps with a waiting-time distribution which is well fitted by a truncated power law. At lower temperatures the rotational correlation times are decoupled from the viscosity.
We present mode-coupling equations for the description of the slow dynamics observed in supercooled molecular liquids close to the glass transition. The mode-coupling theory (MCT) originally formulated to study the slow relaxation in simple atomic liquids, and then extended to the analysis of liquids composed by linear molecules, is here generalized to systems of arbitrarily shaped, rigid molecules. We compare the predictions of the theory for the $q$-vector dependence of the molecular nonergodicity parameters, calculated by solving numerically the molecular MCT equations in two different appr…
We investigate to what extend the replica-exchange Monte Carlo method is able to equilibrate a simple liquid in its supercooled state. We find that this method does indeed allow to generate accurately the canonical distribution function even at low temperatures and that its efficiency is about 10-100 times higher than the usual canonical molecular dynamics simulation.
We develop a phenomenological vector model of polar liquids capable to describe aqueous interactions of macroscopic bodies. It is shown that a strong, long-range and orientationally dependent interaction between macroscopic objects appears as a result of competition between short-range (hydrogen bonding) and the long-range dipole-dipole interactions of the solvent molecules. Spontaneous polarization of molecular dipoles next to a hydrophobic boundaries leads to formation of globally ordered network of hydrogen-bonded molecules with ferroelectric properties. The proposed vector model naturally …
Attractive bonding interactions between molecules typically have inherent conservation laws which influence the statistical properties of such systems in terms of corresponding sum rules. We considered lattice water as an example and enunciated the consequences of the sum rule through a general computational procedure called "Molecular mean field" theory. Fluctuations about mean field are computed and many of the liquid properties have been deduced and compared with Monte Carlo simulation, molecular dynamics and experimental results. Large correlation lengths are seen to be a consequence of th…
We introduce a semi-schematic mode-coupling model to describe the slow dynamics in molecular liquids, retaining explicitly only the description of the center of mass degrees of freedom. Angular degrees of freedom are condensed in a q-vector independent coupling parameter. We compare the time and q-dependence of the density fluctuation correlators with numerical data from a 250 ns long molecular dynamics simulation. Notwithstanding the choice of a network-forming liquid as a model for comparing theory and simulation, the model describes the main static and dynamic features of the relaxation in …
Enormous enhancement in the viscosity of a liquid near its glass transition is generally connected to the growing many-body static correlations near the transition, often coined as `amorphous ordering'. Estimating the length scales of such correlations in different glass-forming liquids is highly important to unravel the physics of glass formation. Experiments on molecular glass-forming liquids become pivotal in this scenario as the viscosity grows several folds ($\sim 10^{14}$), simulations or colloidal glass experiments fail to access the long-time scales required. Here we design an experime…
We present static and dynamic properties of molecular correlation functions S_{lmn,l'm'n'}(q,t) in a simulated supercooled liquid of water molecules, as a preliminary effort in the direction of solving the molecular mode coupling theory (MMCT) equations for supercooled molecular liquids. The temperature and time dependence of various molecular correlation functions, calculated from 250 ns long molecular dynamics simulations, show the characteristic patterns predicted by MMCT and shed light on the driving mechanism responsible for the slowing down of the molecular dynamics. We also discuss the …
We present the results of an analytical theory and simulations of the field inside a cavity created in a dipolar liquid placed in a uniform external electric field. The analytical theory shows that the limit of continuum electrostatics is reached through a singularity in the microscopic response function responsible for a non-decaying longitudinal polarization wave. Fields in microscopic cavities are much different from macroscopic predictions, and low-polarity dielectrics are predicted to have a continuum limit distinct from the solution of Maxwell's equations. Computer Monte Carlo simulation…
We extend our statistical mechanical theory of the glass transition from examples consisting of point particles to molecular liquids with internal degrees of freedom. As before, the fundamental assertion is that super-cooled liquids are ergodic, although becoming very viscous at lower temperatures, and are therefore describable in principle by statistical mechanics. The theory is based on analyzing the local neighborhoods of each molecule, and a statistical mechanical weight is assigned to every possible local organization. This results in an approximate theory that is in very good agreement w…
Liquid-liquid phase separation of liquids exhibiting interconversion between alternative states has been proposed as an underlying mechanism for fluid polyamorphism, and may be of relevance to protein function and intracellular organization. However, molecular-level insight into the interplay between competing forces that can drive or restrict phase separation in interconverting fluids remains elusive. Here, we utilize an off-lattice model of enantiomers with tunable chiral interconversion and interaction properties to elucidate the physics underlying the stabilization and tunability of phase …
The evaluation of the long term stability of a material requires the estimation of its long-time dynamics. For amorphous materials such as structural glasses, it has proven difficult to predict the long-time dynamics starting from static measurements. Here we consider how long one needs to monitor the dynamics of a structural glass to predict its long--time features. We present a detailed characterization of the statistical features of the single-particle intermittent motion of structural glasses, and show that single--particle jumps are the irreversible events leading to the relaxation of the…
We present results of theoretical description of ultrasonic phenomena in molecular liquids. In particular, we are interested in the development of microscopical, i.e., statistical-mechanical framework capable to explain the long living puzzle of the excess ultrasonic absorption in liquids. Typically, ultrasonic wave in a liquid can be generated by applying the periodically alternating external pressure with the angular frequency that corresponds to the ultrasound. If the perturbation introduced by such process is weak - its statistical-mechanical treatment can be done with the use of the linea…
We combine molecular dynamics simulations of deformations at the submicron scale with a continuum fracture mechanics calculation for the onset of crack propagation to predict the macroscopic fracture toughness of amorphous glassy polymers. Key ingredients in this multiscale approach are the elastic properties of polymer crazes and the stress at which craze fibrils fail through chain pullout or scission. Our results are in quantitative agreement with dimensionless ratios that describe experimental polymers and their variation with temperature, polymer length and polymer rigidity.
For a deeply supercooled liquid near its glass transition temperature, we suggest a possible way to connect the temperature dependence of its molar excess entropy to that of its viscosity by constructing a macroscopic model, where the deeply supercooled liquid is assumed to be a mixture of solid-like and liquid-like micro regions. In this model, we assume that the mole fraction x of the liquid-like micro regions tends to zero as the temperature T of the liquid is decreased and extrapolated to a temperature Tg*, which we assume to be below but close to the lowest glass transition temperature Tg…
Liquid-liquid transition is an intriguing phenomenon in which a liquid transforms into another liquid via the first-order transition. For molecular liquids, however, it always takes place in a supercooled liquid state metastable against crystallization, which has led to a number of serious debates concerning its origin: liquid-liquid transition vs. unusual nano-crystal formation. Thus, there have so far been no single example free from such debates. Here we show the first firm experimental evidence that the transition is truly liquid-liquid transition and not nano-crystallization for a molecul…
Using 2D numerical simulations as well as analytical modelling, we show how slow viscoelastic dynamics of aqueous foam are linked to coarsening induced intermittent bubble rearrangements. The macroscopic strain rate is expressed in terms of mesoscopic dynamics where local rearrangements are represented by strain fields induced by force dipoles. We relate these dipoles quantitatively to local geometrical features of the corresponding bubble rearrangements. We also explain how applying a small macroscopic stress biases the outcome of coarsening induced rearrangements.
The synchronized molecular dynamics simulation via macroscopic heat and momentum transfer is proposed for the non-isothermal flow behaviors of complex fluids. In this method, the molecular dynamics simulations are assigned to small fluid elements to calculate the local stresses and temperatures and are synchronized at certain time intervals to satisfy the macroscopic heat- and momentum- transport equations. This method is applied to the lubrication of a polymeric liquid composed of short chains with ten beads between parallel plates. The rheological properties and conformation of polymer chain…
Accurate prediction of a gas solubility in a liquid is crucial in many areas of chemistry, and a detailed understanding of the molecular mechanism of the gas solvation continues to be an active area of research. Here, we extend the idea of constant chemical potential molecular dynamics (CμMD) approach to the calculation of the gas solubility in the liquid under constant gas chemical potential conditions. As a representative example, we utilize this method to calculate the isothermal solubility of carbon dioxide in water. Additionally, we provide microscopic insight into the mechanism of solvat…
The charging and dissolution of mineral surfaces in contact with flowing liquids are ubiquitous in nature, as most minerals in water spontaneously acquire charge and dissolve. Mineral dissolution has been studied extensively under equilibrium conditions, even though non-equilibrium phenomena are pervasive and substantially affect the mineral-water interface. Here we demonstrate using interface-specific spectroscopy that liquid flow along a calcium fluoride surface creates a reversible, spatial charge gradient, with decreasing surface charge downstream of the flow. The surface charge gradient c…
The Cassie-Wenzel transition of a symmetric binary liquid mixture in contact with a nano-corrugated wall is studied. The corrugation consists of a periodic array of nano-pits with square cross sections. The substrate potential is the sum over Lennard-Jones interactions, describing the pairwise interaction between the wall particles $C$ and the fluid particles. The liquid is composed of two species of particles, $A$ and $B$, which have the same size and equal $A - A$ and $B - B$ interactions. The liquid particles interact between each other also via $A - B$ Lennard-Jones potentials. We have emp…
A broad variety of liquids conform to density scaling: relaxation times expressed as a function of the ratio of temperature to density, the latter raised to a material constant γ. For atomic liquids interacting only through simple pair potentials, the exponent γ is very nearly equal to n/3, where n is the steepness of the intermolecular potential, while for molecular liquids having rigid bonds and built using the same interatomic potential, γ>n/3. We find that for this class of molecular liquids γ=n/δ, where the parameter δ relates the intermolecular distance to the density along an isomorph (…
We analyze thermodynamics of water samples confined in nanopores and prove that although the freezing temperature can be dramatically lower, the suppression of the ice nucleation leading to the freezing temperature depression is a truly macroscopic effect rather than a consequence of microscopic interactions. The freezing transition itself is a truly collective phenomenon described by a macroscopic order parameter (the nearly homogeneous density of the liquid within the pore away from the pores wall) exactly in the same way as in the bulk liquid. The thermodynamics properties of the confined a…
The phase behaviour and dynamics of molecular ionic liquids are studied using primitive models and extensive computer simulations. The models account for size disparity between cation and anion, charge location on the cation, and cation-shape anisotropy, which are all prominent features of important materials such as room-temperature ionic liquids. The vapour-liquid phase diagrams are determined using high-precision Monte Carlo simulations, setting the scene for in-depth studies of ion dynamics in the liquid state. Molecular dynamics simulations are used to explore the structure, single-partic…
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…
We report the observation of a distinct correlation between the kinetic fragility index $m$ and the reduced Arrhenius crossover temperature $θ_A = T_A/T_g$ in various glass-forming liquids, identifying three distinguishable groups. In particular, for 11 glass-forming metallic liquids, we universally observe a crossover in the mean diffusion coefficient from high-temperature Arrhenius to low-temperature super-Arrhenius behavior at approximately $θ_A \approx 2$ which is in the stable liquid phases. In contrast, for fragile molecular liquids, this crossover occurs at much lower $θ_A \approx 1.4$ …
We report an ab-initio simulation of liquid Indium in a wide range of pressures and temperatures. We calculate equation of state, thermal expansion and compressibility coefficients. The structure of the system is analyzed by radial distribution functions and structure factors. The results are compared with available experimental data.
The Gordian knot of density-functional theories for classical molecular liquids remains finding an accurate free-energy functional in terms of the densities of the atomic sites of the molecules. Following Kohn and Sham, we show how to solve this problem by considering noninteracting molecules in a set of effective potentials. This shift in perspective leads to an accurate and computationally tractable description in terms of simple three-dimensional functions. We also treat both the linear- and saturation- dielectric responses of polar systems, presenting liquid hydrogen chloride as a case stu…
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.
Wet granular materials in a quasi-static steady state shear flow have been studied with discrete particle simulations. Macroscopic quantities, consistent with the conservation laws of continuum theory, are obtained by time averaging and spatial coarse-graining. Initial studies involve understanding the effect of liquid content and liquid properties like the surface tension on the macroscopic quantities. Two parameters of the liquid bridge contact model have been studied as the constitutive parameters that define the structure of this model (i) the rupture distance of the liquid bridge model, w…
The viscoelasticity of a two-dimensional liquid strongly-coupled dusty plasma is studied experimentally, without macroscopic shear. Positions and velocities of the dust particles, measured by video microscopy, are used as the inputs to the generalized Green-Kubo relation to obtain the complex viscosity $η(ω)$. The real part of $η(ω)$ (which corresponds to dissipation) diminishes gradually with frequency, while the imaginary part (which corresponds to elasticity) is peaked at a frequency below the 2D dusty plasma frequency. The viscoelastic approximation is found to accurately describe the 2D e…
A new symplectic time-reversible algorithm for numerical integration of the equations of motion in magnetic liquids is proposed. It is tested and applied to molecular dynamics simulations of a Heisenberg spin fluid. We show that the algorithm exactly conserves spin lengths and can be used with much larger time steps than those inherent in standard predictor-corrector schemes. The results obtained for time correlation functions demonstrate the evident dynamic interplay between the liquid and magnetic subsystems.
First steps towards developing a new perturbation theory for molecular liquids are taken. By choosing a new form of splitting the site-site potential functions between molecules, we will get a set of atomic fluids as the reference system with known structure and thermodynamics. The perturbative part of the potential function is then expanded up to two terms. The excess Helmholtz free energy of the system is then obtained for three computable contributions. The derivation shows that the excess Helmholtz free energy has nothing to do with intra-atomic potentials, all contributions come merely fr…
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…
Results from molecular dynamics simulations of two viscous molecular model liquids -- the Lewis-Wahnstrom model of ortho-terphenyl and an asymmetric dumbbell model -- are reported. We demonstrate that the liquids have a ``hidden'' approximate scale invariance: Equilibrium potential energy fluctuations are accurately described by inverse power law (IPL) potentials, the radial distribution functions are accurately reproduced by the IPL's, and the radial distribution functions obey the IPL predicted scaling properties to a good approximation. IPL scaling of the dynamics also applies -- with the s…
Molecular dynamics simulations (mds) were carried out to investigate the reorientational motion of a rigid (fixed bond length), asymmetric diatomic molecule in the liquid and glassy states. In the latter the molecule reorients via large-angle jumps, which we identify with the Johari-Goldstein (JG) dynamics. This relaxation process has a broad distribution of relaxation times, and at least deeply in the glass state, the mobility of a given molecule remains fixed over time; that is, there is no dynamic exchange among molecules. Interestingly, the JG relaxation time for a molecule does not depend…
The frequency dependent specific heat has been measured under pressure for the molecular glass forming liquid 5-polyphenyl-4-ether in the viscous regime close to the glass transition. The temperature and pressure dependence of the characteristic timescale associated with the specific heat is compared to the equivalent timescale from dielectric spectroscopy performed under identical conditions. It is shown that the ratio between the two timescales is independent of both temperature and pressure. This observation is non-trivial and demonstrates the existence of specially simple molecular liquids…
Based on previous works on polymers by Bauer et al. [Phys, Rev. B (2000)], this paper describes a capacitative method for measuring the dynamical expansion coefficient of a viscous liquid. Data are presented for the glass-forming liquid tetramethyl tetraphenyl trisiloxane (DC704) in the ultraviscous regime. Compared to the method of Bauer et al. the dynamical range has been extended by making time-domain experiments and by making very small and fast temperature steps. The modelling of the experiment presented in this paper includes the situation where the capacitor is not full because the liqu…
Molecular dynamics simulations have been performed on pure liquid water, aqueous solutions of sodium chloride, and polymer solutions exposed to a strong external electric field with the goal to gain molecular insight into the structural response to the field. Several simulation methodologies have been used to elucidate the molecular mechanisms of the processes leading to the formation of liquid bridges and jets (in the production of nanofibers). It is shown that in the established nanoscale structures, the molecules form a chain with their dipole moments oriented parallel to the applied field …
Understanding the retention of hydrogen isotopes in liquid metals, such as lithium and tin, is of great importance in designing a liquid plasma-facing component in fusion reactors. However, experimental diffusivity data of hydrogen isotopes in liquid metals are still limited or controversial. We employ first-principles molecular dynamics simulations to predict diffusion coefficients of deuterium in liquid tin at temperatures ranging from 573 to 1673 K. Our simulations indicate faster diffusion of deuterium in liquid tin than the self-diffusivity of tin. In addition, we find that the structural…
By means of multiscale molecular simulations, we show that telechelic-star polymers are a simple, robust and tunable system, which hierarchically self-assembles first into soft-patchy particles and then into targeted crystalline structures. The self-aggregating patchy behavior can be fully controlled by the number of arms per star and by the fraction of attractive monomeric units at the free ends of the arms. Such self-assembled soft-patchy particles while forming, upon augmenting density, gel-like percolating networks and stable ordered structures, preserve properties as particle size, number…
We perform molecular-dynamics simulations of a molecular system in supercooled states for different values of inertia parameters to provide evidence that the long-time dynamics depends only on the equilibrium structure. This observation is consistent with the prediction of the mode-coupling theory for the glass transition and with the hypothesis that the potential energy-landscape controls the slow dynamics. We also find that dynamical properties at intermediate wavenumber depend on the spatial correlation of the molecule's geometrical center.
Microscopic understanding of low-frequency molecular motions in liquids has been a longstanding goal in soft-matter science. So far, such low-frequency motions have mostly been accessed indirectly by off-resonant optical pulses. A more direct approach would be to interrogate the dynamic structure of liquids with terahertz (THz) radiation. Here, we provide evidence that resonant excitation with intense THz pulses is capable of driving reorientational-librational modes of aprotic polar liquids through coupling to the permanent molecular dipole moments. We observe a hallmark of this enhanced coup…
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…
The mean-square displacement (MSD) was measured by neutron scattering at various temperatures and pressures for a number of molecular glass-forming liquids. The MSD is invariant along the glass-transition line at the pressure studied, thus establishing an ``intrinsic'' Lindemann criterion for any given liquid. A one-to-one connection between the MSD's temperature dependence and the liquid's fragility is found when the MSD is evaluated on a time scale of approximately 4 nanoseconds, but does not hold when the MSD is evaluated at shorter times. The findings are discussed in terms of the elastic …
