Friction coefficient, solvent

The first successful molecular model of polymer dynamics was developed by Rouse. The chain in the Rouse model is represented as N beads connected by springs of root-mean-square size b, as shown in Fig. 8.2. The beads in the Rouse model only interact with each other through the connecting springs. Each bead is characterized by its own independent friction with friction coefficient (. Solvent is assumed to be freely draining through the chain as it moves. 

Predicting the solvent or density dependence of rate constants by equation (A3.6.29) or equation (A3.6.31) requires the same ingredients as the calculation of TST rate constants plus an estimate of and a suitable model for the friction coefficient y and its density dependence. While in the framework of molecular dynamics simulations it may be worthwhile to numerically calculate friction coefficients from the average of the relevant time correlation fiinctions, for practical purposes in the analysis of kinetic data it is much more convenient and instructive to use experimentally detemiined macroscopic solvent parameters. 

In the Smoluchowski limit, one usually assumes that the Stokes-Einstein relation (Dq//r7)a = C holds, which fonns the basis of taking the solvent viscosity as a measure for the zero-frequency friction coefficient appearing in Kramers expressions. Here C is a constant whose exact value depends on the type of boundary conditions used in deriving Stokes law. It follows that the diffiision coefficient ratio is given by ... 

Multidimensionality may also manifest itself in the rate coefficient as a consequence of anisotropy of the friction coefficient [M]- Weak friction transverse to the minimum energy reaction path causes a significant reduction of the effective friction and leads to a much weaker dependence of the rate constant on solvent viscosity. These conclusions based on two-dimensional models also have been shown to hold for the general multidimensional case [M, 59, and 61]. 

To conclude this section it should be pointed out again that the friction coefficient has been considered to be frequency independent as implied in assuming a Markov process, and that zero-frequency friction as represented by solvent viscosity is an adequate parameter to describe the effect of friction on observed reaction rates. 

Here, y is the friction coefficient of the solvent, in units of ps and Rj is the random force imparted to the solute atoms by the solvent. The friction coefficient is related to the diffusion constant D of the solvent by Einstein s relation y = kgT/mD. The random force is calculated as a random number, taken from a Gaussian distribu-... 

Second, we take account of the frictional drag as the solute molecule moves through the solvent. The frictional force is taken to be proportional to the velocity of the particle, with a proportionality constant called the friction coefficient... 

In this equation, % is a proportionality factor known as the bead-solvent friction coefficient which purports to account in some kind of average way for the complex molecular interactions as the polymer segments (schematized by the bead) move about in the solvent. Following Stokes law of drag resistance, this friction coefficient is usually given as = 67trisa, with a equal to the bead radius. 

Fig. 3.7a,b Friction coefficients as function of solvent Reynolds number Rewat in (n) adiabatic flow, and (b) diabatic flow. Reprinted from Hetsroni et al. (2004) with permission... 

For heterogeneous media composed of solvent and fibers, it was proposed to treat the fiber array as an effective medium, where the hydrodynamic drag is characterized by only one parameter, i.e., Darcy s permeability. This hydrodynamic parameter can be experimentally determined or estimated based upon the structural details of the network [297]. Using Brinkman s equation [49] to compute the drag on a sphere, and combining it with Einstein s equation relating the diffusion and friction coefficients, the following expression was obtained ... 

The frictional coefficient varies with concentration, but at infinite dilution it reduces to the coefficient (/o) for an isolated polymer molecule moving through the surrounding fluid unperturbed by movements of other polymer molecules (see Chap. XIV). At finite concentrations, however, the motion of the solvent in the vicinity of a given polymer molecule is affected by others nearby binary encounters (as well as ones of higher order) between polymer molecules contribute also to the observed frictional effects. The influence of these interactions will persist to very low concentrations owing to the relatively large effective volume of a polymer molecule, to which attention has been directed repeatedly in this chapter. Since the sedimentation con-stant depends inversely on the frictional coefficient, s must also depend bn concentration. 

Equations (29), (30), and (10) might be applied to the elucidation of the frictional coefficient in a manner paralleling the procedure applied to the intrinsic viscosity. One should then determine/o (from sedimentation or from diffusion measurements extrapolated to infinite dilution) in a -solvent in order to find the value of Kf, and so forth. Instead of following this procedure, one may compare observed frictional coefficients with intrinsic viscosities, advantage being taken of the relationships already established for the viscosity. Eliminating from Eqs. (18) and (23) we obtain ... 

The friction coefficient is one of the essential elements in the Langevin description of Brownian motion. The derivation of the Langevin equation from the microscopic equations of motion provides a Green-Kubo expression for this transport coefficient. Its computation entails a number of subtle features. Consider a Brownian (B) particle with mass M in a bath of N solvent molecules with mass m. The generalized Langevin equation for the momentum P of the B... 

Equation (75) shows that (u(t) is an exponentially decaying function for long times with a decay constant /p. For very massive B particles M N mN with M/mN = q = const, the decay rate should vary as 1 /N since p = mNq/ (q + 1). The time-dependent friction coefficient (u(t) for a B particle interacting with the mesoscopic solvent molecules through repulsive LJ potentials... 

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... 

The Langevin dynamics method simulates the effect of individual solvent molecules through the noise W, which is assumed to be Gaussian. The friction coefficient r is related to the autocorrelation function of W through the fluctuation-dissipation theorem,... 

Here, 7 is the friction coefficient and Si is a Gaussian random force uncorrelated in time satisfying the fluctuation dissipation theorem, (Si(0)S (t)) = 2mrykBT6(t) [21], where 6(t) is the Dirac delta function. The random force is thought to stem from fast and uncorrelated collisions of the particle with solvent atoms. The above equation of motion, often used to describe the dynamics of particles immersed in a solvent, can be solved numerically in small time steps, a procedure called Brownian dynamics [22], Each Brownian dynamics step consists of a deterministic part depending on the force derived from the potential energy and a random displacement SqR caused by the integrated effect of the random force... 

Hardness measurements of non-metallic solids are influenced by environmental factors. These have been studied extensively by Westwood (Westwood et al., 1981) and others. However, the evidence is that most, if not all, of the observed effects result from changes in the indenter/specimen friction coefficient caused by adsorption. Under ambient conditions, water vapor is commonly adsorped (Hanneman and Westbrook, 1968). In the presence of various liquids both solvents and solutes are adsorped. Since the effects are not intrinsic to the specimens, they will not be discussed further here. 

The time dependent friction coefficient, per solute mass p, is related to the fluctuating forces exerted by the solvent on the solute coordinate x through their time correlation function ... 

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