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<p>External electric fields have proven to be an effective tool in catalysis, on par with
pressure and temperature, affecting the thermodynamics and kinetics of a reaction.
However, fields in molecules are complicated heterogeneous vector objects, and there
is no universal recipe for grasping the exact features of these fields that implicate reactivity. Herein, we demonstrate that topological features of the heterogeneous electric
field within the reactant state, as well as of the quantum mechanical electron density –
a scalar reporter on the field experienced by the system – can be identified as rigorous
descriptors of the reactivity to follow. We scrutinize specifically the Diels-Alder reaction. Its 3-D nature and the lack of a singular directionality of charge movement upon
barrier crossing makes the effect of the electric field not obvious. We show that the
electric field topology around the dienophile double bond, and the associated changes
in the topology of the electron density in this bond are predictors of the reaction barrier. They are also the metrics by which to rationalize and predict how the external field would inhibit or enhance the reaction. The findings pave the way toward designing external fields for catalysis, as well as reading the reactivity without an explicit
mechanistic interrogation, for a variety of reactions. </p>
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Corrigendum: Oriented Electric Fields Accelerate Diels–Alder Reactions and Control the
endo
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exo
Selectivity
