Interaction of anions with perfluoro aromatic compounds

Area of Science:

• Computational chemistry
• Physical chemistry

Background:

• Anion-aromatic interactions are crucial in various chemical processes.
• Perfluoroaromatic compounds offer unique electronic properties for such interactions.

Purpose of the Study:

• To investigate the binding energies and structural characteristics of anions interacting with perfluoroaromatic systems.
• To compare the efficacy of Density Functional Theory (DFT) and Møller-Plesset perturbation theory (MP2) methods in modeling these interactions.

Main Methods:

• Ab initio calculations using DFT (B3LYP/6-31++G**) and MP2 (MP2/6-31++G**, MP2/6-311++G**) levels of theory.
• Analysis of interaction energies, distances, and electron density distributions using Atoms in Molecules (AIM) theory.

Main Results:

• Anions form stable complexes with perfluoroaromatic compounds, interacting via their pi-electron clouds.
• Interaction energies range from -8 to -19 kcal mol(-1), with MP2 methods yielding stronger interactions than B3LYP.
• AIM analysis revealed diverse electron density topologies dependent on the specific aromatic system.

Conclusions:

• Both DFT and MP2 methods can model anion-perfluoroaromatic interactions, but MP2 provides more accurate interaction energies.
• The nature of the perfluoroaromatic system significantly influences the interaction topology and strength.
• This study provides valuable insights into non-covalent interactions involving perfluorinated aromatic systems.