Reactive atomistic simulations of Diels-Alder reactions: The importance of molecular rotations.
- Rivero U Department of Chemistry, University of Basel, Klingelbergstrasse 80, 4056 Basel, Switzerland.
- Unke OT Department of Chemistry, University of Basel, Klingelbergstrasse 80, 4056 Basel, Switzerland.
- Meuwly M Department of Chemistry, University of Basel, Klingelbergstrasse 80, 4056 Basel, Switzerland.
- Willitsch S Department of Chemistry, University of Basel, Klingelbergstrasse 80, 4056 Basel, Switzerland.
- 2019-09-16
Published in:
- The Journal of chemical physics. - 2019
English
The Diels-Alder reaction between 2,3-dibromo-1,3-butadiene and maleic anhydride has been studied by means of multisurface adiabatic reactive molecular dynamics and the PhysNet neural network architecture. This system is used as a prototype to explore the concertedness, synchronicity, and possible ways of promotion of Diels-Alder reactions. Analysis of the minimum dynamic path indicates that rotational energy is crucial (∼65%) to drive the system toward the transition state in addition to collision energy (∼20%). Comparison with the reaction of butadiene and maleic anhydride shows that the presence of bromine substituents in the diene accentuates the importance of rotational excitation to promote the reaction. At the high total energies at which reactive events are recorded, the reaction is found to be direct and mostly synchronous.
- Language
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- English
- Open access status
- green
- Identifiers
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- DOI 10.1063/1.5114981
- PMID 31521066
- Persistent URL
- https://sonar.ch/global/documents/92616
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