Hot molecules—off the beaten path

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Science  03 Oct 2014:
Vol. 346, Issue 6205, pp. 30-31
DOI: 10.1126/science.1259119

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Much as a weary hiker would take the most level path to avoid unnecessary exertion, chemical reactions are generally assumed to proceed from reactants to products along the “minimum energy path” (MEP) through the potential energy surface (PES) that describes the barriers encountered as bonds break and form. In recent years, however, theoretical and experimental advances have allowed us to see more deeply into the dynamics of energized molecules, and there is growing recognition that a highly excited molecule is more like a wingsuit diver who sails over the PES, roaming to new valleys and sometimes landing in unexpected terrain (1). Such non-MEP dynamics may well be the rule rather than the exception for hot molecules. On page 61 of this issue, Lu et al. (2) illustrate this point in the observation of an unexpected dissociation pathway to O2 from isolated, highly excited CO2 molecules.