Evaluation of Electron Density Shifts in Noncovalent Interactions

Area of Science:

• Computational chemistry
• Quantum chemistry
• Molecular modeling

Background:

• Electron density shift (EDS) is a valuable concept for understanding molecular interactions.
• Quantitative evaluation of EDS maps has been limited, hindering deeper insights.

Purpose of the Study:

• To quantitatively evaluate electron density shift (EDS) maps in various molecular complexes.
• To establish correlations between EDS values and key chemical properties.
• To explore the utility of EDS in systems exhibiting cooperative effects.

Main Methods:

• Quantitative analysis of EDS maps.
• Evaluation of EDS maps at different cutoff values.
• Correlation analysis with interaction energies (Eint), intermolecular distances, bond critical points, and LMOEDA energy decomposition terms.

Main Results:

• Total EDS maps showed good correlation with interaction energies, intermolecular distances, bond critical points, and LMOEDA terms.
• EDS maps at varying cutoffs also correlated well with interaction energies.
• EDS maps and their values demonstrated a correlation with interaction energies in systems with cooperative effects.

Conclusions:

• Quantitative evaluation of EDS maps provides reliable correlations with various chemical descriptors.
• EDS mapping is a promising tool for analyzing molecular interactions, especially in systems with cooperative effects.
• This work presents the first quantitative evaluation of EDS, opening new avenues for computational chemistry research.