Transition-state theory for reactions

Poliak E, Tucker S C and Berne B J 1990 Variational transition state theory for reaction rates in dissipative systems Phys. Rev. Lett. 65 1399... 

Poliak E 1990 Variational transition state theory for activated rate processes J. Chem. Phys. 93 1116 Poliak E 1991 Variational transition state theory for reactions in condensed phases J. Phys. Chem. 95 533 Frishman A and Poliak E 1992 Canonical variational transition state theory for dissipative systems application to generalized Langevin equations J. Chem. Phys. 96 8877... 

Occasionally, the rates of bimolecular reactions are observed to exhibit negative temperature dependencies, i.e., their rates decrease with increasing temperature. This counterintuitive situation can be explained via the transition state theory for reactions with no activation energy harriers that is, preexponential terms can exhibit negative temperature dependencies for polyatomic reactions as a consequence of partition function considerations (see, for example, Table 5.2 in Moore and Pearson, 1981). However, another plausible explanation involves the formation of a bound intermediate complex (Fontijn and Zellner, 1983 Mozurkewich and Benson, 1984). To... 

Transition State Theory for Reactions in Supercritical Fluids... 

So, the values of the parameters found with the transition state theory for reactions in condense matter do lead to a consistency in thermodynamic and... 

E. Poliak, S. C. Tucker, and B. J. Berne, Phys. Rev. Lett., 65, 1399 (1990). Variational Transition State Theory for Reaction Rates in Dissipative Systems. 

Quantum chemical calculation of transition state theory for reaction (5.2) has been reported by Balakrishnan and Billing (1996), and the obtained theoretical value agreed with the above experimental value reasonably well. According to the theoretical calculation, excess energy released by the large exothermicity is retained in one of the produced O2 exclusively, which is formed as vibrationally highly excited molecule with up to v = 27. 

TRANSITION-STATE THEORY FOR REACTIONS ON SURFACES 10.4.1 Unimolecular reactions... 

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