Strong collision limit, defined

When using the temperature dependence of the nuclear spin-spin or nuclear spin-lattice relaxation rate to study molecular motion, as is the case with the surface diffusion we are dealing with here, there exist soolled strong and weak collision limits. Different mathematical relationships are needed to describe these limits. Consider the nuclear spin-spin relaxation rate (1 / T2) as measured by a conventional Hahn-echo pulse sequence, and suppose that Aa> is the amplitude of the local field fluctuation responsible for relaxation. Also assume that r is the correlation time for the motion, say a jump, which causes the local field to fluctuate. The strong collision limit is defined such that... 

The simple collision theory for bimolecular gas phase reactions is usually introduced to students in the early stages of their courses in chemical kinetics. They learn that the discrepancy between the rate constants calculated by use of this model and the experimentally determined values may be interpreted in terms of a steric factor, which is defined to be the ratio of the experimental to the calculated rate constants Despite its inherent limitations, the collision theory introduces the idea that molecular orientation (molecular shape) may play a role in chemical reactivity. We now have experimental evidence that molecular orientation plays a crucial role in many collision processes ranging from photoionization to thermal energy chemical reactions. Usually, processes involve a statistical distribution of orientations, and information about orientation requirements must be inferred from indirect experiments. Over the last 25 years, two methods have been developed for orienting molecules prior to collision (1) orientation by state selection in inhomogeneous electric fields, which will be discussed in this chapter, and (2) bmte force orientation of polar molecules in extremely strong electric fields. Several chemical reactions have been studied with one of the reagents oriented prior to collision. ... 

The impact of bath molecules on the atoms of the molecule of interest cannot be treated as impulsive because the strong binding forces of chemical bonds places a significant fraction of the vibrational sjjectrum of the molecule above the collisional bandwidth, broadly defined as the reciprocal of the duration of a collision. Thus collisional vibrational relaxation and excitation are inefficient relative to rotational relaxation. Binary collision theory is well develojjed at the microcanonical level because of the its importance in chemical reactions. The relationship to the friction is of interest, " primarily because stochastic treatments have the potential of bridging the gas-phase limit of resolved binary collisions and the liquid phase where collective phenomena of the solvent can preclude interpretation in terms of binary collisions. 

The reader may be surprised not to And a Reynolds number defined speciflcally for the disperse phase. This is because the disperse-phase viscosity is well defined only for Knp 1 (i.e. the collision-dominated or hydrodynamic regime). In this limit, Vp oc oc Knp/Map so that the disperse-phase Reynolds number would be proportional to Map/Krip when Map < 1. However, in many gas-particle flows the disperse-phase Knudsen number will not be small, even for ap 0.1, because the granular temperature (and hence the collision frequency) will be strongly reduced by drag and inelastic collisions. In comparison, molecular gases at standard temperature and pressure have KUp 1 even though the volume fraction occupied by the molecules is on the order of 0.001. This fact can be... 

It is important to point out that the limits of the intermediate case may be defined only in an operational way and depend on the accuracy of experiment. If the S-I2 and /1-/2 couplings are weak, the I2 continuum may be neglected and, in the first approximation, the system may be considered as a small molecule. On the other hand, a strong /j-lj coupling dissolves the /j levels in the I2 continuum. Therefore, deviations fi-om the statistical behavior may be insignificant. The interaction with the environment (collisions) shifts the same molecule from one case to another a small molecule collisionally coupled to the kinetic energy continua behaves as an intermediate or statistical system (see below Section III,E,2). 

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