Molecular simulation of loading dependent slow diffusion in confined systems

An extension to transition state theory is presented that is capable of computing quantitatively the diffusivity of adsorbed molecules in confined systems at nonzero loading. This extension to traditional transition state theory yields a diffusivity in excellent agreement with that obtained by conventional molecular dynamics simulations. While molecular dynamics calculations are limited to relatively fast diffusing molecules or small rigid molecules, our approach extends the range of accessible time scales significantly beyond currently available methods. It is applicable in any system containing free energy barriers and for any type of guest molecule.     

Incommensurate diffusion in confined systems

Molecular simulations corroborate the existence of the disputed window effect, i.e., an increase in diffusion rate by orders of magnitude when the alkane chain length increases so that the shape of the alkane is no longer commensurate with that of a zeolite cage. This window effect is shown to be characteristic for molecular sieves with pore openings that approach the diameter of the adsorbate. Furthermore, the physical compatibility between the adsorbate and the adsorbent has a direct effect on the heat of adsorption, the Henry coefficients, the activation energy, and the frequency factors.     

Effects of ultrasonic treatment on zeolite NaA synthesized from by-product silica

The synthesis of zeolite NaA from silica by-product was carried out in the presence of 20 kHz ultrasound at room temperature. Zeolites obtained in this type of synthesis were compared to zeolites obtained by performing conventional static syntheses under similar conditions. The sonication effects on zeolite NaA synthesis were characterized by phase identification, crystallinity etc. The effects of different parameters such as crystallization time and initial materials preparation methods on the crystallinity and morphology of the synthesized zeolites were investigated. The final products were characterized by XRD and FT-IR. It was possible to obtain crystalline zeolite NaA from by-product silica in the presence of ultrasound.     

Acetylene diffusion in Na-Y zeolite

Study of diffusivity of acetylene adsorbed in Na-Y zeolite by quasi-elastic neutron scattering (QENS) measurements at temperatures of 300, 325 and 350 K is reported. A model in which the acetylene molecules undergo random-walk diffusion characterized by a Gaussian distribution of jump lengths inside zeolite cages describes the data consistently. The diffusion constant, residence time between jumps and root mean square jump length are determined.     

Prediction of adsorption of xenon in zeolite NaA with molecular density functional theory

The Tarazona model of molecular density functional theory is used to determine the adsorption isotherm and the density distribution of xenon atoms in zeolite NaA. We consider the alpha cage of NaA to be fully three-dimensional and we introduce a basis set for the density distribution to make the solution computationally tractable. The results of this density functional theory model are compared to previous results of grand canonical Monte Carlo simulations for the same system.We dedicate this paper to Professor Herbert Wagner, whose excellent contributions to density functional theory typify his valuable role in the advancement of statistical physics     

Ion-exchange of monovalent and bivalent cations with NaA zeolite membranes : a molecular dynamics study

Molecular simulations using the method of molecular dynamics have been carried out to study the dynamics and energetics of ion exchanges between monovalent and bivalent cations in supercritical and subcritical (liquid) electrolyte solutions (here Li⁺, and Ca⁺⁺ in aqueous solutions of LiCl and CaCl₂) and an ion exchange membrane (NaA zeolite) using direct simulations of up to a nanosecond or more. NaA zeolites are widely used in many commercial ion-exchange processes including detergents. Results show that with appropriate driving forces, such ion exchange processes can be clearly witnessed and investigated using molecular simulations at these timescales, especially for supercritical solutions. An attempt is made to understand the phenomenon of ion exchange at the molecular level. Results have shown that the ion-exchange process is primarily energetically driven and entropic forces do not appear to be playing a significant role in the exchanges observed. For supercritical LiCl solutions, small differences were found between the energy of the Li⁺ inside and outside the membrane. In contrast, for Na⁺ there was a considerable energetic advantage in being outside the membrane, making the overall exchange process energetically favourable. In subcritical (liquid) LiCl solutions an exchange was found to be more favourable energetically than supercritical solutions. For Ca⁺⁺ similar trends were observed, except the differences in the energies were much larger (compared to the corresponding Li⁺ exchanges), making them more energetically efficient, as has also been observed experimentally. In addition to clarifying the molecular basis for these exchanges, simulations can also potentially be very useful to determine the behaviour (e.g. state dependence, etc.) of hydrodynamic parameters commonly used to characterize ion-exchange processes at a fundamental molecular level, and to determine if the hydrodynamic equations used for ion-exchange processes are applicable to nano-systems that can be studied using simulations.     

Polaritons in confined systems

Polaritons in confined systems are introduced and their dispersion is calculated. The amount of squeezing of confined excitons-polaritons in GaAs quantum wells is evaluated.     

Anisotropic memory effects in confined colloidal diffusion

The motion of an optically trapped sphere constrained by the vicinity of a wall is investigated at times where hydrodynamic memory is significant. First, we quantify, in bulk, the influence of confinement arising from the trapping potential on the sphere's velocity autocorrelation function C(t). Next, we study the splitting of C(t) into C_{parallel}(t) and C_{perpendicular}(t), when the sphere is approached towards a surface. Thereby, we monitor the crossover from a slow t{-3/2} long-time tail, away from the wall, to a faster t{-5/2} decay, due to the subtle interplay between hydrodynamic backflow and wall effects. Finally, we discuss the resulting asymmetric time-dependent diffusion coefficients.     

Electromodulation spectroscopy of confined systems

The convolution formalism of Aspnes and Rowe for the dielectric function in the presence of an electric field is applied to electromodulation spectroscopy of confined systems. It is shown that for isolated confined systems where excitonic effects are not important, electromodulation spectroscopy leads to first derivative like optical features of two dimensional critical points. For superlattices in weak fields (neglecting excitonic interactions), the familiar third derivative forms of Aspnes and Rowe are applicable. In contrast, when moderate and high electric fields are applied to superlattices, electromodulation spectroscopy will exhibit optical features characteristic of first derivative line shapes. This phenomenon arises because the electric field causes the envelope functions of the electron and hole states to become spatially localized. The importance of excitons and their inhomogeneous broadening to the experimentally observed line shapes are considered.     

Labyrinth patterns in confined granular-fluid systems

A random, labyrinthine pattern emerges during slow drainage of a granular-fluid system in two-dimensional confinement. Compacted grains are pushed ahead of the fluid-air interface, which becomes unstable due to a competition between capillary forces and the frictional stress mobilized by grain-grain contact networks. We reproduce the pattern formation process in numerical simulations and present an analytical treatment that predicts the characteristic length scale of the labyrinth structure. The pattern length scale decreases with increasing volume fraction of grains in the system and increases with the system thickness.     

Drift and diffusion of a confined semiflexible chain

We study the transverse and longitudinal linear response function of rigid chains subjected to an external force. Our main concern are stiff polymers confined in narrow pores with diameter less than their persistence length. We explicitly consider confinement in a transverse harmonic potential and generalize results by scaling arguments. Our results describe the drift of the filament under an external force, time evolution of the filament shape, and filament diffusion. Diffusion of a confined filament resembles the celebrated reptation process for flexible chains, albeit with distinct kinetic exponents. The limiting case of stiff free filaments is also mentioned.     

Contrasting friction and diffusion in molecularly thin confined films

We study, using fluorescence correlation spectroscopy, translational diffusion in molecularly thin liquids confined within a surface forces apparatus. The diffusion coefficient decreases exponentially from the edges towards the center of the Hertzian contact and further suggests the presence of a small number of distinct diffusion processes. This holds alike a crystallizable fluid (OMCTS) and a glass-former (1,2-propane diol), both of which displayed static friction. We conclude that friction, the average of an ensemble of molecules, masked massively heterogeneous molecular mobility.     

Limited slowdown of endocrine-disruptor diffusion in confined fluid lipid membranes

Self-diffusion rates of lipids and trapped bisphenol A (BPA) are determined in various sizes of confined but fluid membranes by high-field-gradient NMR at 600 MHz. Micelles and vesicles of 3- to 400-nm diameters are used as model membranes to get an insight into the molecular diffusion in such soft environments. The slowdown of BPA and lipid motions is leveled off in 100- and 400-nm vesicles, although the hydrodynamic continuum model gives the aggregate motion slowed inversely to the aggregate size. Instead, the limited motion is related to the intra-membrane fluidity.     

Structure of intercalated Cs in zeolite ITQ-4: an array of metal ions and correlated electrons confined in a pseudo-1D nanoporous host

The presence of Cs+ ions in the pseudo-1D nanopores of zeolite ITQ-4, Si32O64, is confirmed by x-ray diffraction and atomic pair distribution function analysis. Inside the nanopores the Cs+ ions are found to assemble in zigzag chains and thus form an extended, positively charged sublattice providing charge balance for a low-density electron gas also confined to the nanopores.     

Electron correlation energy in confined two-electron systems

Radial, angular and total correlation energies are calculated for four two-electron systems with atomic numbers Z=0-3 confined within an impenetrable sphere of radius R. We report accurate results for the non-relativistic, restricted Hartree-Fock and radial limit energies over a range of confinement radii from 0.05-10a₀. At small R, the correlation energies approach limiting values that are independent of Z while at intermediate R, systems with Z?1 exhibit a characteristic maximum in the correlation energy resulting from an increase in the angular correlation energy which is offset by a decrease in the radial correlation energy.     

Steplike currents in confined two dimensional systems

In a confined two dimensional system of non-interacting electrons in a normal constant magnetic field, the current is calculated along the sample as a response to an electric field in the same direction which is switched on and then off. The resulting stationary current is shown to be a step-like function of the electron density.     

两电介质间慢速原子的吸收特性

从理论上研究了在不考虑Fabry-Perot效应时两电介质间原子蒸汽膜的吸收光谱,发现在很多情形下表现为Dicke窄化结构的谱线与入射角、膜的厚度和入射波长的比值L/λ有关.我们也讨论了当L/λ=1/2时,吸收峰和带宽相对于入射角的变化.     

Suppression of quantum scattering in strongly confined systems

We demonstrate that scattering of particles strongly interacting in three dimensions (3D) can be suppressed at low energies in a quasi-one-dimensional (1D) confinement. The underlying mechanism is the interference of the s- and p-wave scattering contributions with large s- and p-wave 3D scattering lengths being a necessary prerequisite. This low-dimensional quantum scattering effect might be useful in "interacting" quasi-1D ultracold atomic gases, guided atom interferometry, and impurity scattering in strongly confined quantum wire-based electronic devices.     

Onset of diffusive behavior in confined transport systems

We investigate the onset of diffusive behavior in polygonal channels for disks of finite size, modeling simple microporous membranes. It is well established that the point-particle case displays anomalous transport, because of slow correlation decay in the absence of defocusing collisions. We investigate which features of point-particle transport survive in the case of finite-sized particles (which undergo defocusing collisions). A similar question was investigated by Lansel, Porter, and Bunimovich [Chaos 16, 013129 (2006)], who found that certain integrals of motion and multiple ergodic components, characteristic of the point-particle case, remain in "mushroom"-like systems with few finite-sized particles. We quantify the time scales over which the transport of disks shows features typical of the point particles, or is driven toward diffusive behavior. In particular, we find that interparticle collisions drive the system toward diffusive behavior more strongly than defocusing boundary collisions. We illustrate how, and at what stage, typical thermodynamic behavior (consistent with kinetic theory) is observed, as particle numbers grow and mean free paths diminish. These results have both applied (e.g., nanotechnological) and theoretical interest.