Directional Diels–Alder cycloadditions of isoelectronic graphene and hexagonal boron nitride in oriented external electric fields: reaction axis rule vs. polarization axis rule

We introduced the distinct catalytic mechanisms of the oriented-external-electric-fields-promoted DA reactions of graphene and hexagonal boron nitride. The different responses to fields can be elucidated from the different charge transfer characters.

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Charge transfer in paraffinic hydrocarbons under the influence of external electric fields

Transactions of the Faraday Society ◽

10.1039/tf9706603090 ◽

1970 ◽

Vol 66 ◽

pp. 3090 ◽

Cited By ~ 9

Author(s):

R. J. Fleming

Keyword(s):

Charge Transfer ◽

Electric Fields ◽

External Electric Fields

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Tuning the inter-molecular charge transfer, second-order nonlinear optical and absorption spectra properties of a π-dimer under an external electric field

Physical Chemistry Chemical Physics ◽

10.1039/c7cp06412h ◽

2017 ◽

Vol 19 (47) ◽

pp. 31958-31964 ◽

Cited By ~ 9

Author(s):

Feng-Wei Gao ◽

Hong-liang Xu ◽

Zhong-Min Su

Keyword(s):

Charge Transfer ◽

Electric Field ◽

Electric Fields ◽

Nonlinear Optical ◽

Stability Control ◽

External Electric Fields ◽

Optical Responses ◽

Molecular Charge ◽

Spectra Properties ◽

The Stability

Different strengths of external electric fields enhance the stability, control the inter-molecular charge transfer and strengthen the nonlinear optical responses of a π-dimer.

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Heterogeneous Intramolecular Electric Field as a Descriptor of Diels-Alder Reactivity

10.26434/chemrxiv.13266704.v1 ◽

2020 ◽

Author(s):

Matthew Hennefarth ◽

Anastassia N. Alexandrova

Keyword(s):

Electric Field ◽

Electron Density ◽

Electric Fields ◽

Alder Reaction ◽

Diels Alder ◽

Charge Movement ◽

External Electric Fields ◽

Topological Features ◽

Diels Alder Reaction ◽

Kinetics Of

<div> <div> <div> <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> </div> </div> </div>

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