Hydrodynamic microscopic

Although in principle the microscopic Hamiltonian contains the infonnation necessary to describe the phase separation kinetics, in practice the large number of degrees of freedom in the system makes it necessary to construct a reduced description. Generally, a subset of slowly varying macrovariables, such as the hydrodynamic modes, is a usefiil starting point. The equation of motion of the macrovariables can, in principle, be derived from the microscopic... 

R), i.e. there is no effect due to caging of the encounter complex in the common solvation shell. There exist numerous modifications and extensions of this basic theory that not only involve different initial and boundary conditions, but also the inclusion of microscopic structural aspects [31]. Among these are hydrodynamic repulsion at short distances that may be modelled, for example, by a distance-dependent diffiision coefficient... 

The relation between the microscopic friction acting on a molecule during its motion in a solvent enviromnent and macroscopic bulk solvent viscosity is a key problem affecting the rates of many reactions in condensed phase. The sequence of steps leading from friction to diflfiision coefficient to viscosity is based on the general validity of the Stokes-Einstein relation and the concept of describing friction by hydrodynamic as opposed to microscopic models involving local solvent structure. In the hydrodynamic limit the effect of solvent friction on, for example, rotational relaxation times of a solute molecule is [ ]... 

Existing statistical methods permit prediction of macroscopic results of the processes without complete description of the microscopic phenomena. They are helpful in establishing the hydrodynamic relations of liquid flow through porous bodies, the evaluation of filtration quality with pore clogging, description of particle distributions and in obtaining geometrical parameters of random layers of solid particles. 

Molecular dynamics, in contrast to MC simulations, is a typical model in which hydrodynamic effects are incorporated in the behavior of polymer solutions and may be properly accounted for. In the so-called nonequilibrium molecular dynamics method [54], Newton s equations of a (classical) many-particle problem are iteratively solved whereby quantities of both macroscopic and microscopic interest are expressed in terms of the configurational quantities such as the space coordinates or velocities of all particles. In addition, shear flow may be imposed by the homogeneous shear flow algorithm of Evans [56]. 

The function / incorporates the screening effect of the surfactant, and is the surfactant density. The exponent x can be derived from the observation that the total interface area at late times should be proportional to p. In two dimensions, this implies R t) oc 1/ps and hence x = /n. The scaling form (20) was found to describe consistently data from Langevin simulations of systems with conserved order parameter (with n = 1/3) [217], systems which evolve according to hydrodynamic equations (with n = 1/2) [218], and also data from molecular dynamics of a microscopic off-lattice model (with n= 1/2) [155]. The data collapse has not been quite as good in Langevin simulations which include thermal noise [218]. 

These apparent restrictions in size and length of simulation time of the fully quantum-mechanical methods or molecular-dynamics methods with continuous degrees of freedom in real space are the basic reason why the direct simulation of lattice models of the Ising type or of solid-on-solid type is still the most popular technique to simulate crystal growth processes. Consequently, a substantial part of this article will deal with scientific problems on those time and length scales which are simultaneously accessible by the experimental STM methods on one hand and by Monte Carlo lattice simulations on the other hand. Even these methods, however, are too microscopic to incorporate the boundary conditions from the laboratory set-up into the models in a reahstic way. Therefore one uses phenomenological models of the phase-field or sharp-interface type, and finally even finite-element methods, to treat the diffusion transport and hydrodynamic convections which control a reahstic crystal growth process from the melt on an industrial scale. 

In this section we show how the fundamental equations of hydrodynamics — namely, the continuity equation (equation 9.3), Euler s equation (equation 9.7) and the Navier-Stokes equation (equation 9.16) - can all be recovered from the Boltzman equation by exploiting the fact that in any microscopic collision there are dynamical quantities that are always conserved namely (for spinless particles), mass, momentum and energy. The derivations in this section follow mostly [huangk63]. 

Introduction.—Statistical physics deals with the relation between the macroscopic laws that describe the internal state of a system and the dynamics of the interactions of its microscopic constituents. The derivation of the nonequilibrium macroscopic laws, such as those of hydrodynamics, from the microscopic laws has not been developed as generally as in the equilibrium case (the derivation of thermodynamic relations by equilibrium statistical mechanics). The microscopic analysis of nonequilibrium phenomena, however, has achieved a considerable degree of success for the particular case of dilute gases. In this case, the kinetic theory, or transport theory, allows one to relate the transport of matter or of energy, for example (as in diffusion, or heat flow, respectively), to the mechanics of the molecules that make up the system. 

Before beginning a size determination, it is customary to look at the material, preferably under a microscope. This examination reveals the approx size range and distribution of the particles, and especially the shapes of the particles and the degree of aggregation. If microscopic examination reveals that the ratios between max and min diameters of individual particles do not exceed 4, and indirect technique for particle size distribution based on sedimentation or elutria-tion may be used. Sedimentation techniques for particle size determination were first used by Hall (Ref 2) in 1904, He showed that the rate of fall of individual particles in a fluid was directly related to the particle size by the hydrodynamic... 

In fluid dynamics the behavior in this system is described by the full set of hydrodynamic equations. This behavior can be characterized by the Reynolds number. Re, which is the ratio of characteristic flow scales to viscosity scales. We recall that the Reynolds number is a measure of the dominating terms in the Navier-Stokes equation and, if the Reynolds number is small, linear terms will dominate if it is large, nonlinear terms will dominate. In this system, the nonlinear term, (u V)u, serves to convert linear momentum into angular momentum. This phenomena is evidenced by the appearance of two counter-rotating vortices or eddies immediately behind the obstacle. Experiments and numerical integration of the Navier-Stokes equations predict the formation of these vortices at the length scale of the obstacle. Further, they predict that the distance between the vortex center and the obstacle is proportional to the Reynolds number. All these have been observed in our 2-dimensional flow system obstructed by a thermal plate at microscopic scales. ... 

The results presented here are quite remarkable. The theory underlying derivation of the hydrodynamic equations assumes that all gradients and forces acting on the fluid are small. The MD fluids are under the influence of extremely large gradients and forces. Yet, we find results which are in both qualitative and quantitative agreement with macroscopic predictions. The appearance of spatial structure on such a small scale (10 cm) provides strong indications that fluid dynamics can be understood from a microscopic viewpoint. 

The q(T) can be independently measured by a viscometer and the value of y is determined by the PCS measurement at a certain temperature (typically 21 22 °C). Under the condition that the hydrodynamic diameter of the probe molecule is constant in the temperature range examined, we can obtain the temperature of the confocal area. It is worth noting that the present method estimates average temperature inside the confocal volume of the microscopic system because ECS provides the average value of the translational diffusion velocity over multiple fluorescent molecules passing through the sampling area. 

Perhaps the best starting point in a review of the nonequilibrium field, and certainly the work that most directly influenced the present theory, is Onsager s celebrated 1931 paper on the reciprocal relations [10]. This showed that the symmetry of the linear hydrodynamic transport matrix was a consequence of the time reversibility of Hamilton s equations of motion. This is an early example of the overlap between macroscopic thermodynamics and microscopic statistical mechanics. The consequences of time reversibility play an essential role in the present nonequilibrium theory, and in various fluctuation and work theorems to be discussed shortly. 

The friction coefficient of a large B particle with radius ct in a fluid with viscosity r is well known and is given by the Stokes law, Q, = 67tT CT for stick boundary conditions or ( = 4jit ct for slip boundary conditions. For smaller particles, kinetic and mode coupling theories, as well as considerations based on microscopic boundary layers, show that the friction coefficient can be written approximately in terms of microscopic and hydrodynamic contributions as ( 1 = (,(H 1 + (,/( 1. The physical basis of this form can be understood as follows for a B particle with radius ct a hydrodynamic description of the solvent should... 

It is known that polymer dynamics is strongly influenced by hydrodynamic interactions. When viewed on a microscopic level, a polymer is made from molecular groups with dimensions in the angstrom range. Many of these monomer units are in close proximity both because of the connectivity of the chain and the fact that the polymer may adopt complicated conformations in solution. Polymers are solvated by a large number of solvent molecules whose molecular dimensions are comparable to those of the monomer units. These features make the full treatment of hydrodynamic interactions for polymer solutions very difficult. 

P. J. Hoogerbrugge and J. M. V. A. Koelman, Simulating microscopic hydrodynamic phenomena with dissipative particle dynamics, Europhys. Lett. 19, 155 (1992). 

It is well-known that the electrophoretic effect involves the hydrodynamical properties of the solvent in a very crucial way for this reason, the theory of this effect is rather difficult. However, using a Brownian approximation for the ions, we have been able to obtain recently a microscopic description of this effect. This problem, together with the more general question of long-range hydrodynamical correlations, is discussed in Section VI. 

However, the present formulation has the advantage of furnishing a mathematically rigorous foundation to the classical theory and is readily extended to other physical situations, like plasmas32 and semiconductors. Also, it allows us to give a microscopic foundation to the theory of the electrophoretic effect, which is much more delicate because it involves the difficult question of long-range hydrodynamical correlations this point will be the object of Section VI. 

VI. MICROSCOPIC THEORY OF ELECTROPHORESIS AN EXAMPLE OF HYDRODYNAMICAL LONG-RANGE... 

This type of argument furnishes in fact the microscopic justification of hydrodynamical equations. 

Fig. 6 (a) Schematic illustration of a flow cytometer used in a suspension array. The sample microspheres are hydrodynamically focused in a fluidic system and read-out by two laser beams. Laser 1 excites the encoding dyes and the fluorescence is detected at two wavelengths. Laser 2 is used to quantify the analyte, (b) Scheme of randomly ordered bead array concept. Beads are pooled and adsorbed into the etched wells of an optical fiber, (c) Scheme of randomly-ordered sedimentation array. A set of encoded microspheres is added to the analyte solution. Subsequent to binding of the analyte, microparticles sediment and assemble at the transparent bottom of a sample tube generating a randomly ordered array. This array is evaluated by microscope optics and a CCD-camera. Reproduced with permission from Refs. [85] and [101]. Copyright 1999, 2008 American Chemical Society... 

Originally, the concept of the Prandtl boundary layer was developed for hydraulically even bodies. It is assumed that any characteristic length L on the particle surface is much greater than the thickness (<5hl) of the boundary layer itself (L > Ojil) Provided this assumption is fulfilled, the concept can be adapted to curved bodies and spheres, including real drug particles. Furthermore, the classical ( macroscopic ) concept of the hydrodynamic boundary layer is valid solely for high Reynolds numbers of Re>104 (14,15). This constraint was overcome for the microscopic hydrodynamics of dissolving particles by the convective diffusion theory (9). 

Figure 9 shows a magnification (x7500) of the smooth and regular surface area indicated in Figure 8. The length of the edges of the cube was of the order of about 200-300 pm. The particle surface appeared to be smooth. Nevertheless, small craters and hills of the order of about 0.5-3 pm have to be taken into consideration. The observed cavitations and protrusion on the particle surfaces may cause perturbations, change the nature of the hydrodynamic boundary layer, and hence increase dissolution. Furthermore, as was confirmed by these microscopic observations, small...

---