Evaluating the Ability of External Electric Fields to Accelerate Reactions in Solution

Area of Science:

• Physical Chemistry
• Chemical Kinetics
• Computational Chemistry

Background:

• External electric fields (EEFs) offer a potential route for catalytic control in chemical reactions.
• Understanding EEF effects requires detailed investigation of reaction mechanisms and experimental conditions.

Purpose of the Study:

• To investigate the catalytic effects of EEFs on the Menshutkin reaction and Chapman rearrangement in solution.
• To determine if current experimental setups can achieve EEF-driven catalysis for these reactions.

Main Methods:

• Utilized a scanning tunneling microscope-based break-junction (STM-BJ) setup for reaction monitoring.
• Employed high-performance liquid chromatography with UV detection (HPLC-UV) and UPLC-quadrupole time-of-flight mass spectrometry (UPLC-q-ToF-MS) for rate analysis.
• Performed density functional theory (DFT) calculations to model reaction pathways and energy landscapes.

Main Results:

• No significant rate enhancement was observed for either the Menshutkin reaction or Chapman rearrangement under ambient conditions.
• DFT calculations revealed that electric field-induced changes in reactant orientation and activation energy minimization are critical for catalysis.
• Current experimental field strengths and setups were found to be insufficient for catalyzing the studied reactions.

Conclusions:

• The efficacy of EEF catalysis is highly dependent on specific reaction characteristics, including reactant orientation and activation energy.
• Further research with optimized experimental parameters is needed to explore the potential of EEF catalysis.
• The findings highlight the importance of careful selection of reaction candidates and experimental conditions for EEF-driven chemical transformations.