An algorithm to find the optimal oriented external electrostatic field for annihilating a reaction barrier in a...

Area of Science:

• Computational Chemistry
• Theoretical Chemistry
• Chemical Physics

Background:

• Oriented external electric fields (OEEFs) are increasingly studied for controlling chemical reactivity.
• Predicting the optimal OEEF (oOEEF) to lower reaction energy barriers is a key challenge.

Purpose of the Study:

• To present a novel model for finding the oOEEF for a given reaction.
• To enable precise control over chemical processes using electric fields.

Main Methods:

• Developed a model based on catastrophe and optimum control theories.
• Constructed an effective potential energy surface (PES) using the polarizable molecular electric dipole (PMED) model.
• Identified the optimal barrier breakdown or bond-breaking point (oBBP) on the original PES.

Main Results:

• The oOEEF can be determined by locating the oBBP, a topologically unique point on the PES.
• The oBBP retains its topological properties across different OEEF strengths, unlike traditional transition states.
• The PMED model successfully predicted oOEEFs for a cumulene isomerization and a Huisgen cycloaddition.

Conclusions:

• The developed model provides a robust method for predicting oOEEFs.
• The oBBP is a more relevant structural feature than minima or transition states for OEEF-controlled reactions.
• The PMED model and its implementation offer a valuable tool for computational chemistry research.