Concepedia

Unimolecular Dissociations and Free Radical Recombination Reactions

R. A. Marcus

The Journal of Chemical Physics · 1952 · 924 citations · 3 references

Concepts

TL;DR

Steric and pressure effects in free‑radical recombination depend on the activated complex and are closely linked. This paper extends a prior theory on methyl radical–iodine atom recombination. The authors derive equations for these effects from unimolecular dissociation, extending earlier transition‑state and quasi‑unimolecular theories and introducing a new density‑of‑states expression for high‑energy molecules. Applications indicate that all vibrational modes can transfer energy to excited molecules, highlighting vibrational anharmonicity as a key factor in intramolecular energy transfer.

Abstract

The steric and pressure effects associated with the recombination of free radicals both depend on the nature of the activated complex, and are therefore intimately related. From a consideration of the reverse process of unimolecular dissociation, some equations are derived for these properties using an extension of earlier transition state and quasi-unimolecular theories. The present formalism differs from previous formulations of the latter in a number of ways, particularly in the expression used for the density of quantum states of the high energy molecules. Subsequent applications of the theory tentatively suggest that essentially all vibrational degrees of freedom of these molecules can contribute their energy to the vibrationally excited molecules. Consequently, vibrational anharmonicity would appear to be an important factor in intramolecular energy transfer. The present paper is an extension of a previously developed theory for the recombination of methyl radicals and iodine atoms.

References

3

5.6K citations

The Kinetics of the Recombination of Methyl Radicals and Iodine Atoms.

R. A. Marcus, O. K. Rice · The Journal of Physical Chemistry · 1951

661 citations