Tunneling molecular dynamics in the light of the corpuscular-wave dualism theory

This paper presents the experimental demonstration of the corpuscular-wave dualism theory. The correlation between the de Broglie wavelength related to the thermal motion and the potential barrier width and height is reported. The stochastic jumps of light atoms (hydrogen, deuterium) between two equilibrium sites A and B (identical geometry) occur via different pathways; one pathway is over the barrier (classical dynamics), and the other one is through the barrier (tunneling). On the over-the-barrier pathway, there are no obstacles for the de Broglie waves, and this pathway exists from high to low temperatures up to 0 K because the thermal energy is subjected to the Maxwell distribution and a certain number of particles owns enough energy for the hopping over the barrier. On the tunneling pathway, the particles pass through the barrier, or they are reflected from the barrier. Only particles with the energy lower than barrier heights are able to perform a tunneling hopping. The de Broglie waves related to these energies are longer than the barrier width. The Schr?dinger equation is applied to calculate the rate constant of tunneling dynamics. The Maxwell distribution of the thermal energy has been taken into account to calculate the tunneling rate constant. The equations for the total spectral density of complex motion derived earlier by us together with the expression for the tunneling rate constant, derived in the present paper, are used in analysis of the temperature dependence of deuteron spin-lattice relaxation of the ammonium ion in the deuterated analogue of ammonium hexachloroplumbate ((ND4)2PbCl6). It has been established that the equation CpTtun = EH (thermal energy equals activation energy), where Cp is the molar heat capacity (temperature-dependent, known from literature), determines directly the low temperature Ttun at which the de Broglie wavelength, lambdadeBroglie, related to the thermal energy, CpT, is equal to the potential barrier width, L. Above Ttun, the lambdadeBroglie wavelength related to the CpT energy is shorter than the potential barrier width and not able to overcome the barrier. The activation energy EH equals 7.5 kJ/mol, and therefore, the Ttun temperature for deuterons in ((ND4)2PbCl6 is 55.7 K. The agreement between the potential barrier width following from the simple geometrical calculations (L = 0.722 A) and de Broglie wavelength at Ttun (L = 0.752 A) is good. The temperature plots of the deuteron correlation times for (ND4)2PbCl6 reveal comparable values of the correlation times of the tunneling, (tau(T)), and over-the-barrier jumps (tau(H)) near 34.8 K. Matsuo, on the basis of the molar heat capacity study, found the first-order phase transition at this temperature.     

Electrolyte-dependent multiparticle motion near electrodes in oscillating electric fields

The directed assembly of micrometer-scale particles into hexagonal lattices on electrodes was probed by subjecting them to electric fields oscillating at 100 Hz. Solutions of KOH, NaHCO(3), and KCl were used because previous investigations of particle pair behavior had shown that an electrolyte-dependent phase angle dictates whether two particles aggregate or separate at low frequencies. Here it was found that particle ensembles, aggregating or separating, adopt a 2D hexagonal lattice in both cases; the difference appears in the particle spacing. For electrolytes such as NaHCO(3) and KCl, where two isolated particles aggregate, the gap between particle edges is between 1 and 1.5 particle diameters; in KOH, where two particles tend to separate, the interparticle spacing is several diameters.     

The Existence of Non-negatively Charged Dust Particles in Nonthermal Plasmas

Particles in nonthermal dusty plasmas tend to charge negatively. However several effects can result in a significant fraction of the particles being neutral or positively charged, in which case they can deposit on surfaces that bound the plasma. Monte Carlo charging simulations were conducted to explore the effects of several parameters on the non-negative particle fraction of the stationary particle charge distribution. These simulations accounted for two effects not considered by the orbital motion limited theory of particle charging: single-particle charge limits, which were implemented by calculating electron tunneling currents from particles; and the increase in ion current to particles caused by charge-exchange collisions that occur within a particle’s capture radius. The effects of several parameters were considered, including particle size, in the range 1–10 nm; pressure, ranging from 0.1 to 10 Torr; electron temperature, from 1 to 5 eV; positive ion temperature, from 300 to 700 K; plasma electronegativity, characterized in terms of n ₊/n _e ranging from 1 to 1000; and particle material, either SiO₂ or Si. Within this parameter space, higher non-negative particle fractions are associated with smaller particle size, higher pressure, lower electron temperature, lower positive ion temperature, and higher electronegativity. Additionally, materials with lower electron affinities, such as SiO₂, have higher non-negative particle fractions than materials with lower electron affinities, such as Si.     

Crystallization mechanisms in convective particle assembly

Colloidal particles are continuously assembled into crystalline particle coatings using convective fluid flows. Assembly takes place inside a meniscus on a wetting reservoir. The shape of the meniscus defines the profile of the convective flow and the motion of the particles. We use optical interference microscopy, particle image velocimetry, and particle tracking to analyze the particles' trajectory from the liquid reservoir to the film growth front and inside the deposited film as a function of temperature. Our results indicate a transition from assembly at a static film growth front at high deposition temperatures to assembly in a precursor film with high particle mobility at low deposition temperatures. A simple model that compares the convective drag on the particles to the thermal agitation explains this behavior. Convective assembly mechanisms exhibit a pronounced temperature dependency and require a temperature that provides sufficient evaporation. Capillary mechanisms are nearly temperature independent and govern assembly at lower temperatures. The model fits the experimental data with temperature and particle size as variable parameters and allows prediction of the transition temperatures. While the two mechanisms are markedly different, dried particle films from both assembly regimes exhibit hexagonal particle packings. We show that films assembled by convective mechanisms exhibit greater regularity than those assembled by capillary mechanisms.     

Computational probes of molecular motion in the Lewis-Wahnstrom model for ortho-terphenyl

We use molecular dynamics simulations to investigate translational and rotational diffusion in a rigid three-site model of the fragile glass former ortho-terphenyl, at 260 K< or =T< or =346 K and ambient pressure. An Einstein formulation of rotational motion is presented, which supplements the commonly used Debye model. The latter is shown to break down at supercooled temperatures as the mechanism of molecular reorientation changes from small random steps to large infrequent orientational jumps. We find that the model system exhibits non-Gaussian behavior in translational and rotational motion, which strengthens upon supercooling. Examination of particle mobility reveals spatially heterogeneous dynamics in translation and rotation, with a strong spatial correlation between translationally and rotationally mobile particles. Application of the Einstein formalism to the analysis of translation-rotation decoupling results in a trend opposite to that seen in conventional approaches based on the Debye formalism, namely, an enhancement in the effective rate of rotational motion relative to translation upon supercooling.     

Single particle jumps in a binary Lennard-Jones system below the glass transition

We study a binary Lennard-Jones system below the glass transition with molecular dynamics simulations. To investigate the dynamics we focus on events (jumps) where a particle escapes the cage formed by its neighbors. Using single particle trajectories we define a jump by comparing for each particle its fluctuations with its changes in average position. We find two kinds of jumps: "reversible jumps," where a particle jumps back and forth between two or more average positions, and "irreversible jumps," where a particle does not return to any of its former average positions, i.e., successfully escapes its cage. For all investigated temperatures both kinds of particles jump and both irreversible and reversible jumps occur. With increasing temperature, relaxation is enhanced by an increasing number of jumps and growing jump lengths in position and potential energy. However, the waiting time between two successive jumps is independent of temperature. This temperature independence might be due to aging, which is present in our system. We therefore also present a comparison of simulation data with three different histories. The ratio of irreversible to reversible jumps is also increasing with increasing temperature, which we interpret as a consequence of the increased likelihood of changes in the cages, i.e., a blocking of the "entrance" back into the previous cage. In accordance with this interpretation, the fluctuations both in position and energy are increasing with increasing temperature. A comparison of the fluctuations of jumping particles and nonjumping particles indicates that jumping particles are more mobile even when not jumping. The jumps in energy normalized by their fluctuations are decreasing with increasing temperature, which is consistent with relaxation being increasingly driven by thermal fluctuations. In accordance with subdiffusive behavior are the distributions of waiting times and jump lengths in position.     

Effect of Particle Surface Heating on the Sedimentation Rate

The Stokes and Hadamard-Rybchinsky formulas are generalized, making it possible to take into account the temperature dependence of viscosity in a wide range of temperatures and to calculate the force of resistance to motion and velocity of gravitational fall at arbitrary temperature differences between the particle surface and a remote region.     

Heterogeneity in styrene-butadiene latex films

Low-Tg styrene-butadiene (SB) latex films were investigated by noncontact atomic force microscopy and scanning electric potential microscopy, revealing a number of different morphologies and electric potential patterns across films cast from the same SB latex dispersions under the same conditions. Surface leveling and charge dispersion throughout the films are, thus, restrained even at temperatures above Tg and the minimum film-formation temperature. An unprecedented electric pattern is observed, in which the particle cores are more positive than the contacting particle outer layers. Different packing patterns, including cubic and hexagonal arrays, coexist in neighboring areas. Zonal centrifugation of the SB latex in sucrose density gradient shows that particles cover a broad range of densities. Thus, film surface heterogeneity is at least partly due to particle heterogeneity. Fractal dimensions of topographic profiles are lower than those of the electric potential profiles, showing that charge mobility is much more restrained than polymer chain motion at the film surface and that it imposes a limit to the charged chain-ends motion.     

Dipole moments of symmetrical molecular systems

It is shown that quantization of nuclear motion causes the intrinsic dipole moment of a molecular system to depart from the classical representation, e.g., it is different from zero for symmetrical molecules. A formula is derived for the mean dipole moment ¯p as a function of temperature with allowance for the internal motion of the nuclei, which is functionally related to the dipole moment. Calculations are performed for ammonia with allowance for the inversion splitting, which is due to tunneling between two equivalent equilibrium configurations having their dipole moments in opposite directions. The temperature coefficient of ¯p may be positive or negative, in accordance with the relation between the tunneling frequency and the temperature; the formula usually employed is valid only in the limiting case of low frequencies and high temperatures. A deduction is given for the criterion for instability of the maximally symmetrical configuration with respect to odd nuclear displacements (dipole distortions); this is based on a simple model system having an inversion center, a totally symmetric ground state, and a triply degenerate odd excited state of the T_1u type. The experimental consequences of the results are discussed, as well as the concept of symmetry for a molecular system in which the maximally symmetrical configuration is unstable.     

Temperature dependence of the dynamic mechanical properties of filled polymers

A theory has been developed to explain the jump in the relative modulus of filled polymers near the glass transition temperature T_g and the subsequent decrease in relative modulus at temperatures above the glass transition temperature. The theory is based upon the concept that there are some particle–particle contacts in doublets and in agglomerates containing a larger number of particles. Below T_g motion of particles at the contact points is possible because of the high modulus of the polymer. At T_g particle–particle motion mostly ceases because of the low modulus of the polymer. At higher temperatures, the mismatch in the coefficients of expansion allows some motion to occur at points of contact and slippage may occur at the polymer–particle interfaces, so the modulus decreases. It is shown theoretically and experimentally that both the elastic modulus and the mechanical damping depend upon the nature of the surface of the particles.     

Spin blockade in the conduction of colloidal CdSe nanocrystal films

The conduction of thin films of n-type CdSe colloidal quantum dots is studied at low temperature and under magnetic field. At medium and high magnetic fields (10 T), the films exhibit positive magnetoresistance consistent with the variable range hopping model. At low magnetic field(<0.3 T) but in the strong electric field regime, there is a narrower magnetoresistance of order 10%-15%. The magnetoresistance shows a strong bias dependence, small and positive at low bias, increasing but still positive at higher bias, and turning negative at the highest bias. A similar behavior has been reported recently for thin film organics. Weak localization effects are ruled out. The explanation for the observations is based on spin blockade relaxed by the hyperfine interaction. The weak magnetoresistance at low bias is attributed to the diffusing paths taken by the hopping electrons. At higher bias, the more directed motion of electrons leads to increasingly positive magnetoresistance due to the more effective spin blockade. At the highest bias, the magnetoresistance becomes negative, which is attributed to the increased exchange interaction associated with the shorter tunneling distance.     

Sterically and electrosterically stabilized emulsion polymerization. Kinetics and preparation

The principal subject discussed in the current paper is the radical polymerization in the aqueous emulsions of unsaturated monomers (styrene, alkyl (meth)acrylates, etc.) stabilized by non-ionic and ionic/non-ionic emulsifiers. The sterically and electrosterically stabilized emulsion polymerization is a classical method which allows to prepare polymer lattices with large particles and a narrow particle size distribution. In spite of the similarities between electrostatically and sterically stabilized emulsion polymerizations, there are large differences in the polymerization rate, particle size and nucleation mode due to varying solubility of emulsifiers in oil and water phases, micelle sizes and thickness of the interfacial layer at the particle surface. The well-known Smith-Ewart theory mostly applicable for ionic emulsifier, predicts that the number of particles nucleated is proportional to the concentration of emulsifier up to 0.6. The thin interfacial layer at the particle surface, the large surface area of relatively small polymer particles and high stability of small particles lead to rapid polymerization. In the sterically stabilized emulsion polymerization the reaction order is significantly above 0.6. This was ascribed to limited flocculation of polymer particles at low concentration of emulsifier, due to preferential location of emulsifier in the monomer phase. Polymerization in the large particles deviates from the zero-one approach but the pseudo-bulk kinetics can be operative. The thick interfacial layer can act as a barrier for entering radicals due to which the radical entry efficiency and also the rate of polymerization are depressed. The high oil-solubility of non-ionic emulsifier decreases the initial micellar amount of emulsifier available for particle nucleation, which induces non-stationary state polymerization. The continuous release of emulsifier from the monomer phase and dismantling of the non-micellar aggregates maintained a high level of free emulsifier for additional nucleation. In the mixed ionic/non-ionic emulsifiers, the released non-ionic emulsifier can displace the ionic emulsifier at the particle surface, which then takes part in additional nucleation. The non-stationary state polymerization can be induced by the addition of a small amount of ionic emulsifier or the incorporation of ionic groups onto the particle surface. Considering the ionic sites as no-adsorption sites, the equilibrium adsorption layer can be thought of as consisting of a uniform coverage with holes. The de-organization of the interfacial layer can be increased by interparticle interaction via extended PEO chains--a bridging flocculation mechanism. The low overall activation energy for the sterically stabilized emulsion polymerization resulted from a decreased barrier for entering radicals at high temperature and increased particle flocculation.     

Analysis of particle-wall interactions during particle free fall

In this study, the vertical motion of a particle in a quiescent fluid falling toward a horizontal plane wall is analyzed, based on simplified models. Using the distance between the particle and wall as a parameter, the effects of various forces acting on the particle and the particle motion are examined. Without the colloidal and Brownian forces being included, the velocity of small particles is found to be approximately equal to the inverse of the drag force correction function used in this study as the particle approaches the near-wall region. Colloidal force is added to the particle equation of motion as the particle moves a distance comparable to its size. It is found that the particle might become suspended above or deposited onto the wall, depending on the Hamaker constant, the surface potentials of the particle and wall, and the thickness of the electrical double layer (EDL). For strong EDL repulsive force and weaker van der Waals (VDW) attractive force, the particle will become suspended above the wall at a distance at which the particle velocity is zero. This location is referred to as the equilibrium distance. The equilibrium distance is found to increase with increased in EDL thickness when a repulsive force barrier appears in the colloidal force interaction. For the weak EDL repulsive force and strong VDW attractive force case, the particle can become deposited onto the wall without the Brownian motion effect. The Brownian jump length was found to be very small. Many Brownian jumps would be required in a direction toward the wall for a suspended particle to become deposited.     

Particle dynamics and particle heat and mass transfer in thermal plasmas. Part I. The motion of a single particle without thermal effects

A particle injected into a thermal plasma will experience a number of effects which are not present in an ordinary gas. In this paper effects exerted on the motion of a particle will be reviewed and analyzed in the context of thermal plasma processing of materials. The primary purpose of this paper is an assessment of the relative importance of various effects on particle motion.Computer experiments are described, simulating motion of a spherical particle in a laminar, confined plasma jet or in a turbulent, free plasma jet. Particle sizes range from 5 to 50 µm, and as sample materials alumina and tungsten are considered.The results indicate that (i) the correction term required for the viscous drag coefficient due to strongly varying properties is the most important factor; (ii) non-continuum effects are important for particle sizes <10 µm at atmospheric pressure and these effects will be enhanced for smaller particles and/or reduced pressures; (iii) the Basset history term is negligible, unless relatively large and light particles are considered over long processing distances; (iv) thermophoresis is not crucial for the injection of particles into thermal plasmas; (v) turbulent dispersion becomes important for particle <10 µm in diameter.     

An in situ study of the adsorption behavior of functionalized particles on self-assembled monolayers via different chemical interactions

The formation of particle monolayers by convective assembly was studied in situ with three different kinds of particle-surface interactions: adsorption onto native surfaces, with additional electrostatic interactions, and with supramolecular host-guest interactions. In the first case carboxylate-functionalized polystyrene (PS-COOH) particles were assembled onto native silicon oxide surfaces, in the second PS-COOH onto protonated amino-functionalized (NH3+) self-assembled monolayers (SAMs), and in the third beta-CD-functionalized polystyrene (PS-CD) particles onto beta-CD SAMs with pre-adsorbed ferrocenyl-functionalized dendrimers. The adsorption and desorption behaviors of particles onto and from these surfaces were observed in situ on a horizontal deposition setup, and the packing density and order of the adsorbed particle lattices were compared. The desorption behavior of particles from surfaces was evaluated by reducing the temperature below the dew point, thus initiating water condensation. Particle lattices on native oxide surfaces formed the best hexagonal close packed (hcp) order and could be easily desorbed by reducing the temperature to below the dew point. The electrostatically modified assembly resulted in densely packed, but disordered particle lattices. The specificity and selectivity of the supramolecular assembly process were optimized by the use of ferrocenyl-functionalized dendrimers of low generation and by the introduction of competitive interaction by native beta-CD molecules during the assembly. The fine-tuned supramolecularly formed particle lattices were nearly hcp packed. Both electrostatically and supramolecularly formed lattices of particles were strongly attached to the surfaces and could not be removed by condensation.     

Tunneling dynamics of a double‐well oscillator: Effects of barrier fluctuation and thermal modulation

The tunneling dynamics of a particle moving in a bistable potential with fluctuating barrier is studied. For barriers fluctuating randomly in time we show by exact numerical calculation the significant effect of barrier fluctuation on the tunneling behavior of the particle. At nonzero temperatures the computed tunneling rate constant passes through a maximum when plotted against fluctuation frequency. The resonant frequency (at which the maximum appears) slowly decreases with increase in temperature and attains a constant value at higher temperature and it increases linearly with increase in barrier height of the potential. Another important observation is that in presence of barrier fluctuation the dependence of tunneling rate constant on temperature is strongly guided by the barrier fluctuation frequency. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 93: 280–285, 2003     

Quantification of solid pressure in the concentration polarization (CP) layer of colloidal particles and its impact on ultrafiltration

Here we describe the nature and implications of the "concentration polarization" (CP) layer that is formed during ultrafiltration of colloidal particles using a new approach in which the solid pressure, which arises from inter-particle interactions, and the inherent osmotic pressure are separately considered. The approach makes use of the particle transport mass balance between the convective and diffusive fluxes. The particle convection rate is hindered when inter-particle interactions take effect by reducing the particle velocities while the particle diffusion is solely controlled by the Brownian motion. An increase in solid pressure accounts for the reduction of the water potential caused by the relative motions of the particles and the surrounding water. A cell model is adopted to relate the local solid pressure with the local solid fraction and inter-particle interactions. The inter-particle interactions critically determine the form of particle accumulation (i.e. CP or gel/cake) on the membrane. The Shirato-Darcy equation is employed to relate the rate of increase in solid pressure, the relative liquid velocity and the solid fraction. Numerical integration approaches are employed to quantify the properties of the CP layer during both the development as well as the steady state phases (with steady state normally being achieved in a few minutes). The solid fractions are always no higher than those obtained when the inter-particle interactions are not considered. The decrease of the water potential caused by CP formation leads to the increase of both the solid pressure and the osmotic pressure. The dependence of the solid pressure on the solid fraction is usually stronger than that of the osmotic pressure. It is thus apparent that the solid pressure would be expected to dominate water potential reduction for solid fractions above a certain value though the solid pressure will be negligible when the solid fraction is relatively low.     

Dynamic self-assembly of polymer colloids to form linear patterns

A dynamic self-assembling process is reported which involves drying a droplet of positively charged colloidal suspension on a flat negatively charged hydrophilic surface. This extremely simple method affords lines of colloidal particles with regular 1.5-4.5 microm line spacing and smaller than 2 microm line width over a broad surface area. The ordered region diffracts light to display an iridescent appearance and generates first-order diffraction spots when illuminated by a He-Ne laser. A periodic stick-slip motion of the drying liquid front is observed during the drying process using optical microscopy. The periodic motion must be related to the periodic particle deposition. We propose that the simultaneous deposition of the particles at a fixed distance (i.e., the line spacing) behind the previous line of particles where the contact line is pinned is in turn responsible for the periodic stick-slip motion. The key distinguishing feature of the present system is the attractive interaction between the particles and the surface, which instigates the periodicity of the particle deposition.