Abstract
N. B. Slater has recently discussed this subject1 Some time ago, I treated the same problem2 not in terms of the normal modes of the molecule, but of the individual bonds where the kinetic energy is expressed as a mixed quadratic form and not as a pure sum of squares. The result, then, seems to permit of an easily visualized interpretation, namely, that the rate constant depends only on the force constant of the breaking bond, the energy required to rupture it, and on the two masses of the atoms adjacent to the breaking bond. It does not depend at all on the remainder of the molecule, which simply acts as a temperature bath. Thus the result is the same as for a diatomic molecule for which the temperature-independent constant is found to be exactly equal to its vibrational frequency.
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References
Slater, Nature, 159, 264 (1947).
Pelzer, Z. Elektrodiem., 39, 608 (1933).
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PELZER, H. Absolute Values of the Rates of Unimolecular Reactions. Nature 160, 576 (1947). https://doi.org/10.1038/160576b0
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DOI: https://doi.org/10.1038/160576b0
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