Rice-Ramsberger-Kassel-Marcus theory

In a series of important papers Marcus and coworkers applied the RRKM (Rice-Ramsberger-Kassel-Marcus) theory of unimolecular reactions to the ozone problem in a successful effort to rationalize the MIF s described above (see Historical Vignette 14.1). The 2002 paper of Gao and Marcus (reading list) considered a kinetic scheme which mildly elaborates that of Equation 14.1... 

REMPI RRKM resonant-enhanced multiphoton ionization Rice-Ramsberg-Kassel-Marcus (theory)... 

In the statistical theory of RICE, RAMSBERGER, KASSEL, and MARCUS (RRKM), an equilibrium-energy distribution among the vibrational-rotational degrees of freedom is assumed for both the activated molecule (for which E>E ) and the "activated complex (for which E >E ). Quantum effects, such as sudden change of the electronic sta-... 

Modern unimolecular theory has its origins in the work of Rice, Ramsberger and Kassel [44] who investigated the rate of dissociation of a molecule as a function of energy. Marcus and Rice [44] subsequently extended the theory to take account of quantum mechanical features. This extended theory, referred to as RRKM theory, is currently the most widely used approach and is usually the point of departure for more sophisticated treatments of unimolecular reactions. The key result of RRKM theory is that the microcanonical rate coefficient can be expressed as... 

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