Assumptions and Derivation of the Basic Transition-State Method Expressions

1 Assumptions and Derivation of the Basic Transition-State Method Expressions 

Different formulations of the basic assumptions of the transition state-method are possible. The following most general formulation wiU be considered [339]. 

We shall return to the problem of critical surface choice later and now assume that this problem is somehow solved. The following conditions near are assumed  

Since the system located at the critical surface plays an important part, the notion of the activated complex is introduced. By definition, the activated complex corresponds to the representative point on the critical surface. 

Under these assumptions, the rate constant expression is 

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