Automated Variable Electric-Field DFT Application for Evaluation of Optimally Oriented Electric Fields on Chemical...

Area of Science:

• Computational Chemistry
• Organic Reaction Mechanisms
• Physical Organic Chemistry

Background:

• Oriented electric fields (OEFs) offer theoretical and experimental control over organic reaction rates and selectivity.
• Previous limitations in evaluating reaction sensitivity to OEFs hindered practical synthetic applications.
• OEFs can be applied externally or induced locally to influence chemical transformations.

Purpose of the Study:

• To develop streamlined software for evaluating a reaction's susceptibility to OEF effects.
• To create an accessible tool for non-expert users in computational chemistry.
• To enable efficient assessment of OEFs as catalysts for organic reactions.

Main Methods:

• Development of the Automated Variable Electric-Field DFT Application (A.V.E.D.A.) as an open-source Linux workflow.
• Automated density functional theory (DFT) calculations to optimize structures under varying electric field strengths.
• Analysis of molecular/reaction dipole moments, perturbed geometries, and effective activation energies.

Main Results:

• A.V.E.D.A. automates the evaluation of reaction sensitivity to OEFs with a single command.
• The software successfully assessed ten representative pericyclic reactions.
• Provides key data including field-perturbed geometries and net effective activation energies.

Conclusions:

• A.V.E.D.A. significantly simplifies the assessment of OEF effects on organic reactions.
• The software lowers the barrier for implementing OEFs in synthetic chemistry research.
• Facilitates the exploration of OEFs as a novel catalytic strategy.