Taking the High Road and Getting There Before You

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Science  10 Jun 2011:
Vol. 332, Issue 6035, pp. 1269-1270
DOI: 10.1126/science.1206693

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Advances in experimental or theoretical methodology sometimes reveal that the existing model for a phenomenon under study is actually incorrect or, at best, incomplete. One long-standing model that is being rethought in light of recent results is the transition state theory (TST) model, especially when applied to the selectivity of a chemical reaction—why more of one product forms versus another under a given set of conditions. In the conventional TST model, reactants must scale an energy barrier and pass through a transition state to form stable products. Reactions with lower barriers are usually the favored products. On page 1300 of this issue, Schreiner et al. (1) report that low-temperature reaction of an organic molecule is completely at odds with TST predictions, and that a proper accounting of the quantum-mechanical nature of the nuclei in molecules is needed to explain the results.