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Dynamic Electric Field Complicates Chemical Reactions in Solutions
Yao Kun Lei1, Jun Zhang1, Zhen Zhang2
1Institute of Theoretical and Computational Chemistry, College of Chemistry and Molecular Engineering , Peking University , Beijing 100871 , China.
The Journal of Physical Chemistry Letters
|May 17, 2019
Summary
External electric fields (EEFs) can alter chemical reactions. Dynamic effects are crucial, as EEFs can lower reaction barriers or even create potential wells, leading to complex, solvent-modulated reaction pathways.
Area of Science:
- Physical Chemistry
- Chemical Dynamics
- Computational Chemistry
Background:
- External electric fields (EEFs) influence chemical reactions.
- Time-dependent EEFs and their dynamic effects during fast reactions are not fully understood.
- Understanding electrostatic interactions is key to controlling reaction pathways.
Purpose of the Study:
- To investigate the dynamic effects of external electric fields on chemical reaction mechanisms.
- To explore how electrostatic interactions modify reaction barriers and dynamics.
- To elucidate the role of solvent dynamics in heterogeneous reaction paths.
Main Methods:
- Computational modeling of chemical reactions under external electric fields.
- Analysis of electrostatic interactions and their impact on transition states.
- Simulations of solvent effects on reaction dynamics.
Main Results:
- Electrostatic interactions can reduce reaction barriers and accelerate bonding motions.
- Strong EEFs can create potential wells, altering concerted mechanisms to stepwise ones.
- Solvent dynamics significantly modulate reaction pathways, leading to heterogeneity.
- Excessive transition state stabilization can hinder barrier crossing.
Conclusions:
- Dynamic effects of EEFs play a critical role in chemical reactions, especially during fast processes.
- Solvent-induced charge redistribution and EEF adaptation are crucial for reaction progression.
- Reaction mechanisms and dynamics are highly sensitive to the interplay between EEFs and solvent environments.
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