Exploring the Reactivity of Donor-Acceptor Systems through a Combined Conceptual and Constrained DFT Approach

Area of Science:

• Computational Chemistry
• Theoretical Chemistry
• Quantum Chemistry

Background:

• Conceptual density functional theory (cDFT) provides a framework for understanding chemical reactivity.
• Constrained DFT (CDFT) offers computational efficiency for such studies.

Purpose of the Study:

• To demonstrate that chemical reactivity can be governed by the difference between local interacting chemical potentials of reactants (Edual).
• To investigate the influence of Coulomb and exchange-correlation contributions on Edual.
• To explore the potential energy surfaces of clusters using a Sanderson-like model.

Main Methods:

• Utilizing the computational efficiency of constrained DFT (CDFT).
• Investigating illustrative examples of non-covalent donor-acceptor systems and reactive systems.
• Evaluating the influence of Coulomb and exchange-correlation contributions on Edual.

Main Results:

• Chemical reactivity is governed by Edual, in agreement with Sanderson's equalization principle.
• Edual mimics DFT-computed intermolecular interaction energy profiles for selected systems.
• Sanderson-like models based on classical interactions can explore cluster potential energy surfaces.

Conclusions:

• The study deepens the understanding of cDFT principles.
• The study assesses the efficiency of cDFT in predicting chemical reactivity.
• The findings suggest a simplified approach to exploring potential energy surfaces.