Abstract
A new solution to the master equation relating the rate coefficients for unimolecular, recombination (association) and chemical activation reactions, incorporating weak collision effects, is presented. The solution establishes conditions for the validity of the commonly used procedure of relating the recombination rate coefficient, throughout the falloff regime, to the reverse single-channel unimolecular rate coefficient via the equilibrium constant. In addition, a relationship between the rate coefficient for stabilization in a chemical activation reaction and the reverse multichannel unimolecular dissociation rate coefficient is derived. This result, in conjunction with recently developed methods for fully incorporating angular momentum conservation into the solution of the master equation for unimolecular dissociation, enables both angular momentum and weak collision effects to be accurately incorporated into the solution of the master equation for chemical activation reactions in the falloff regime. Application of this method to a typical ion/molecule chemical activation reaction, that of CH+3 with NH3, illustrates the importance of weak collision and angular momentum effects in this system.
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