Intermolecular interaction potential maps from energy decomposition for interpreting reactivity and intermolecular...

Area of Science:

• Computational Chemistry
• Molecular Modeling
• Chemical Physics

Background:

• Electrostatic potential (ESP) is a common tool for visualizing molecular interactions.
• However, ESP alone is often insufficient to fully capture complex molecular interactions and reactivity.
• A need exists for more comprehensive methods to analyze intermolecular forces.

Purpose of the Study:

• To develop and apply intermolecular interaction potential maps (IMIPs) for a more detailed understanding of molecular interactions and reactivity.
• To overcome the limitations of traditional electrostatic potential (ESP) mapping.
• To provide novel insights into the physical origins and positional preferences of molecular interactions.

Main Methods:

• Developed IMIPs using energy decomposition analysis (EDA) with density functional theory (DFT).
• Constructed IMIPs from probe interactions with molecular fragments (e.g., CH3+, CH3-, benzene) and atomic probes (metals, halides).
• Decomposed interaction potentials into components (electrostatic, orbital, steric) to create component-specific IMIPs.

Main Results:

• Applied IMIPs to diverse systems: cation-π, anion-π, aromatic substitutions, Lewis acid activation, π-stacking, endohedral fullerenes, and organometallics.
• Revealed fundamental insights into positional preferences and physical origins of interactions.
• Demonstrated the superiority of IMIPs over other surface analyses for uncovering interaction details.

Conclusions:

• IMIPs provide a powerful and detailed approach to analyzing molecular interactions and reactivity.
• This method offers unique insights beyond traditional ESP analysis.
• IMIPs are valuable for studying a wide range of chemical phenomena and systems.