General dynamic equation experimental results

As we discussed earlier, the generalized Boltzmann equation leads to a density expansion of the transport coefficients of a dense gas. However, general expressions for transport coefficients of a fluid that are not in the form of an expansion can be derived by another technique, the time correlation function method. This approach has provided a general framework by means of which one can make detailed comparisons between theoretical results, the results of computer-simulated molecular dynamics,and experimental results. ... 

These result from the numerical solution of the dynamic equations (1) - (4) with the relevant rate constants for adsorption/desorp-tion and surface reaction, equilibrium constants and catalyst capacity obtained by independent experimental measurements (no fitting of the periodic data was attempted). The results clearly indicate a general agreement with the experimental data. The simulations are described and discussed in detail elsewhere (, 12)-... 

In Section II, the basic equations of OCT are developed using the methods of variational calculus. Methods for solving the resulting equations are discussed in Section III. Section IV is devoted to a discussion of the Electric Nuclear Bom-Oppenhermer (ENBO) approximation [41, 42]. This approximation provides a practical way of including polarization effects in coherent control calculations of molecular dynamics. In general, such effects are important as high electric fields often occur in the laser pulses used experimentally or predicted theoretically for such processes. The limits of validity of the ENBO approximation are also discussed in this section. 

The more incisive calculation of Springett, et al., (1968) allows the trapped electron wave function to penetrate into the liquid a little, which results in a somewhat modified criterion often quoted as 47r/)y/V02< 0.047 for the stability of the trapped electron. It should be noted that this criterion is also approximate. It predicts correctly the stability of quasi-free electrons in LRGs and the stability of trapped electrons in liquid 3He, 4He, H2, and D2, but not so correctly the stability of delocalized electrons in liquid hydrocarbons (Jortner, 1970). The computed cavity radii are 1.7 nm in 4He at 3 K, 1.1 nm in H2 at 19 K, and 0.75 nm in Ne at 25 K (Davis and Brown, 1975). The calculated cavity radius in liquid He agrees well with the experimental value obtained from mobility measurements using the Stokes equation p = eMriRr], with perfect slip condition, where TJ is liquid viscosity (see Jortner, 1970). Stokes equation is based on fluid dynamics. It predicts the constancy of the product Jit rj, which apparently holds for liquid He but is not expected to be true in general. 

---