Association/Dissociation Processes in Dense Gases.
Annual technical rept. 1 Jul 84-30 Jun 85,
GEORGIA INST OF TECH ATLANTA SCHOOL OF PHYSICS
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A new basic microscopic theory of associationdissociation processes in dense gases has been developed. Expressions for the time-dependent rates R subscript A, Dt for the associationdissociation of atomic or molecular species A and B in a gas M are formulated in terms of the net probability P sub i superscript A, D for associationdissociation of bound energy level i of the pair A-B. A new Variational Principle for these rates is proposed and is applied to ion-ion recombination, as a benchmark, with very successful results. The diffusional theory is examined and it is shown that highly accurate results can be obtained for general mass systems provided the new basic expression introduced here for R sub A,Dt is adopted. The microscopic basis of the mascroscopic Debye-Smoluchowski Equation DSE is examined and analytical expressions for rates are derived for general interactions between A and B. A valuable relationship between the rates of recombination appropriate to the cases of ions generated with uniform frequency within a reaction volume and ions which approach each other from infinite separation is derived.
- Physical Chemistry