Abstract
In ordinary kinetic studies the required activation energy is introduced via intermolecular collisions. When the activation barrier is large, reaction must be run at high temperature or progress is imperceptible. Moreover, thermal activation is quite undiscriminating. Energy is partitioned among the various internal degrees of freedom of the reactants according to a Boltzmann distribution. There is no procedure to concentrate the energy of the reagents in the vibrational degree of freedom which most favors reaction. Furthermore, thermal processes always proceed by low-energy pathways. It is thus not possible, by heating, to select another mode of reaction requiring vastly greater activation energy.
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General References
Photochemistry
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© 1979 Plenum Press, New York
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Jordan, P.C. (1979). Photochemistry. In: Chemical Kinetics and Transport. Springer, Boston, MA. https://doi.org/10.1007/978-1-4615-9098-9_6
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DOI: https://doi.org/10.1007/978-1-4615-9098-9_6
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