Unimolecular reaction kinetics

The Lindemann theory thus has the correct behavior at the high- and low-pressure limits. However, quantitative comparisons between this theory and experiment revealed a number of problems. The remainder of this section discusses more detailed theoretical treatments of unimolecular reaction kinetics. 

RRKM theory represents the state of the art in understanding unimolecular reaction kinetics. However, because of the rigorous treatment of molecular energetics and quantum mechanics, it requires rather sophisticated numerical software to evaluate the rate constant. Computer programs to evaluate RRKM rate expressions are widely available examples are UNIMOL by Gilbert and Smith [143], and a program by Hase and Bunker [166]. 

The study of energy flow in molecules has been largely motivated by its role in unimolecular reaction kinetics, such as the kinetics of conformational... 

Theoretical studies of unimolecular reaction kinetics of polyatomic molecules in a mass spectrometer requires the knowledge of the number of states of a molecule with internal energy E, fV(E). It has been shown by Rosenstock et... 

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