Stochastic theory validity

An interesting, but probably incorrect, application of the probabilistic master equation is the description of chemical kinetics in a dilute gas.5 Instead of using the classical deterministic theory, several investigators have introduced single time functions of the form P(n1,n2,t) where P(nu n2, t) is the probability that there are nl particles of type 1 and n2 particles of type 2 in the system at time t. They use the transition rate A(nt, n2 n2, n2, t) from the state with particles of type 1 and n2 particles of type 2 to the state with nt and n2 particles of types 1 and 2, respectively, at time t. The rates that are used are obtained by assuming that only uncorrelated binary collisions occur in the system. These rates, however, are only correct in the thermodynamic limit for a low density system. In this limit, the Boltzmann equation is valid from which the deterministic theory follows. Thus, there is no reason to attach any physical significance to the differences between the results of the stochastic theory and the deterministic theory.6... 

Pasti, L. Dondi, F. van Hulst, M. Schoenmakers, R Martin, M. Felinger, A. Experimental validation of the stochastic theory of size exclusion chromatography Retention on single and coupled columns. Chromatographia 2003,57 (Suppl ), S171-S186. 

One possibility for this was demonstrated in Chapter 3. If impact theory is still valid in a moderately dense fluid where non-model stochastic perturbation theory has been already found applicable, then evidently the continuation of the theory to liquid densities is justified. This simplest opportunity of unified description of nitrogen isotropic Q-branch from rarefied gas to liquid is validated due to the small enough frequency scale of rotation-vibration interaction. The frequency scales corresponding to IR and anisotropic Raman spectra are much larger. So the common applicability region for perturbation and impact theories hardly exists. The analysis of numerous experimental data proves that in simple (non-associated) systems there are three different scenarios of linear rotator spectral transformation. The IR spectrum in rarefied gas is a P-R doublet with either resolved or unresolved rotational structure. In the process of condensation the following may happen. 

In order to verify which of the above nucleation mechanisms accurately represents hydrate nucleation, it is clear that experimental validation is required. This can then lead to such qualitative models being quantified. However, to date, there is very limited experimental verification of the above hypotheses (labile cluster or local structuring model, or some combination of both models), due to both their stochastic and microscopic nature, and the timescale resolution of most experimental techniques. Without experimental validation, these hypotheses should be considered as only conceptual aids. While the resolution of a nucleation theory is uncertain, the next step of hydrate growth has proved more tenable for experimental evidence, as discussed in Section 3.2. 

In this section we analyze experimental data and make comparisons with theory. Data were obtained for 100 CdSe-ZnS nanocrystals at room temperature.1 We first performed data analysis (similar to standard approach) based on the distribution of on and off times and found that a+= 0.735 0.167 and v = 0.770 0.106,2 for the total duration time T = T = 3600 s (bin size 10 ms, threshold was taken as 0.16 max I(t) for each trajectory). Within error of measurement, a+ a k 0.75. The value of a 0.75 implies that the simple diffusion model with a = 0.5 is not valid in this case. An important issue is whether the exponents vary from one NC to another. In Fig. 13 (top) we show the distribution of a obtained from data analysis of power spectra. The power spectmm method [26] yields a single exponent apSd for each stochastic trajectory (which is in our case a+ a apSd). Figure 13 illustrates that the spread of a in the interval 0 < a < 1 is not large. Numerical simulation of 100 trajectories switching between 1 and 0, with /+ (x) = / (x) and a = 0.8, and with the same number of bins as the experimental trajectories, was performed and the... 

By employing a very strong external field, a gedankexperiment may be set up whereby the natural thermal motion of the molecules is put in competition with the aligning effect of the field. This method reveals some properties of the molecular liquid state which are otherwise hidden. In order to explain the observable effects of the applied fields, it is necessary to use equations of motion more generally valid than those of Benoit. These equations may be incorporated within the general structure of reduced model theory " (RMT) and illustrate the use of RMT in the context of liquid-state molecular dynamics. (Elsewhere in this volume RMT is applied to problems in other fields of physics where consideration of stochastic processes is necessary.) In this chapter modifications to the standard methods are described which enable the detailed study of field-on molecular dynamics. 

A consistently quantum mechanical theory describing the coherent and stochastic dynamics of tetrahedral rotors has not been reported yet. Nevertheless, in the extreme situations where the facile re-orientations involve only one axis, the DQR theory will be rigorously valid also for such rotors. Specifically, if the unique axis is a three-fold axis, the stochastic term will have the same form as in Eq. (8) [or the equivalent form in Eq. (10)]. In the case of a two-fold axis, the AB term such as that in Eq. (5) will be obtained, but with the pair-permutation operator P replaced by the operator R defined above. One can thus reasonably expect that even in the cases where there are more than one facile re-orientation axes, applicability of the phenomenological AB approach will suffer similar restrictions as those specified in Subsection 4.4 for methyl-like rotors. 

It can be objected however that as statistics is able to provide an explanation for many of the systems for which one proposes the influence theory, it dismisses the validity of the proposed approach, which in the best case becomes unnecessary. This is not a correct reasoning. In many eases, a statistical approach may propose a model for a physical phenomenon that can be modeled by another theoretical approach not using statistics. For instance, the area of a target included in a larger and known area may be determined by the measure of the number of hits of a dart launched by a player, assuming a random process in the launch. This is the basis of stochastic methods such... 

The Smith and Ewart-Stockmayer-O Toole treatments [48-50] (see Chapter 4) that are widely used to calculate the average number of free radicals per particle (n) are based on the assumption that the various components of the monomer-swollen latex particles (e.g., monomer, polymer, free radicals, chain transfer agent, etc.) are uniformly distributed within the particle volume. A latex particle in emulsion homopolymerization of styrene involves uniform distribution of monomer and polymer within the particle volume except perhaps for a very thin layer near the particle surface. In the case of free radicals, this uniform distribution would only hold in a stochastic sense. However, as illustrated in Eq. (8.1), free radicals are not distributed uniformly in the latex particles when water-soluble initiators are used to initiate the free radical polymerization. The assumption of uniform distribution of free radicals in the latex particles would be valid only if the particles are very small or chain transfer reactions are the dominate mechanism for producing free radicals. If such a nonuniform free radical distribution hypothesis is accepted, the very basis of the Smith and Ewart-Stockmayer-O Toole methods might be questioned. Despite this potential problem, the Stockmayer-O Toole solutions for the average number of free radicals per particle have been used for kinetic studies of many emulsion polymerization systems. The theories seem to work reasonably well and have been tested extensively with monomers such as styrene. 

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