Limitations of Transition State Theory
In general, TST has provided researchers with a conceptual foundation for understanding how chemical reactions take place. Even though the theory is widely applicable, it does have limitations. For example, when applied to each elementary step of a multi-step reaction, the theory assumes that each intermediate is long-lived enough to reach a Boltzmann distribution of energies before continuing to the next step. When the intermediates are very short-lived, however, then TST fails. In such cases, the momentum of the reaction trajectory from the reactants to the intermediate can carry forward to affect product selectivity (an example of such a reaction is the thermal decomposition of diazaobicyclopentanes, presented by Anslyn and Dougherty).
Transition state theory is also based on the assumption that atomic nuclei behave according to classic mechanics. It is assumed that unless atoms or molecules collide with enough energy to form the transition structure, then the reaction does not occur. However, according to quantum mechanics, for any barrier with a finite amount of energy, there is a possibility that particles can still tunnel across the barrier. With respect to chemical reactions this means that there is a chance that molecules will react even if they do not collide with enough energy to traverse the energy barrier. While this effect is expected to be negligible for reactions with large activation energies, it becomes a more important phenomenon for reactions with relatively low energy barriers, since the tunneling probability increases with decreasing barrier height.
Transition state theory fails for some reactions at high temperature. The theory assumes the reaction system will pass over the lowest energy saddle point on the potential energy surface. While this description is consistent for reactions occurring at relatively low temperatures, at high temperatures, molecules populate higher energy vibrational modes; their motion becomes more complex and collisions may lead to transition states far away from the lowest energy saddle point. This deviation from transition state theory is observed even in the simple exchange reaction between diatomic hydrogen and a hydrogen radical.
Given these limitations, several alternatives to transition state theory have been proposed. A brief discussion of these theories follows.
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