One-to-One Correspondence between Reaction Pathways and Reactive Orbitals.

Area of Science:

• Computational Chemistry
• Theoretical Chemistry
• Quantum Chemistry

Background:

• Chemical reaction theories, including potential energy theory and electronic theory, have historically developed independently.
• Understanding the intricate details of chemical reactions, such as electron transfer and dynamics, remains a key challenge in chemistry.

Purpose of the Study:

• To establish a one-to-one correspondence between reaction pathways in potential energy theory and reactive orbitals in electronic theory.
• To apply the reactive orbital energy method to analyze intrinsic reaction coordinates and global reaction route maps.
• To determine whether chemical reactions are primarily driven by electron transfer or molecular dynamics.

Main Methods:

• Application of the reactive orbital energy method to intrinsic reaction coordinates.
• Utilizing a global reaction route map generated by an automated reaction path search.
• Specification of occupied and unoccupied reactive orbital pairs driving chemical reactions.

Main Results:

• A clear one-to-one correspondence was found between reaction pathways and reactive orbitals.
• The reactive orbital energy method successfully identified electron transfer-driven and dynamics-driven reaction pathways.
• Specific reactive orbital pairs were identified for electron transfer-driven pathways originating from the same molecule.
• The method provided sophisticated interpretations of electronic motions during reactions.

Conclusions:

• The identified one-to-one correspondence is expected to unify the independently developed potential energy and electronic theories of reactions.
• The reactive orbital energy method offers a powerful tool for interpreting and predicting chemical reaction mechanisms.
• This work provides a new framework for understanding the fundamental driving forces behind chemical transformations.