Real-Space Interpretation of Interatomic Charge Transfer and Electron Exchange Effects by Combining Static and...

Area of Science:

• Quantum Chemistry
• Solid-State Physics
• Computational Materials Science

Background:

• Understanding electron behavior is crucial for predicting chemical bonding and material properties.
• Existing models often struggle to accurately capture electron exchange effects in complex systems.

Purpose of the Study:

• To investigate the behavior of one-electron potentials and gradient force fields in crystals.
• To develop a method for partitioning molecules and crystals based on electron density and potentials.
• To explain interatomic charge transfer and electron sharing phenomena.

Main Methods:

• Analysis of Euler equation for electron density and gradient forces.
• Superposition of electrostatic and kinetic potentials with electron density.
• Definition and analysis of atomic (κ-basins) and potential-based (λ-basins) partitioning.
• Examination of zero-flux surfaces and spatial gaps between basins.

Main Results:

• Identified channels of enhanced kinetic potential and saddle points between bonded atoms.
• Developed a partitioning scheme (κ- and λ-basins) that accounts for electron exchange effects.
• Explained interatomic charge transfer and electron sharing via gaps between basin boundaries.
• Proposed a regularity for the relative positions of basin boundaries, correlating them with bond types (hydrogen, covalent, ionic).

Conclusions:

• The κ- and λ-basin partitioning provides a more complete description of electron interactions than κ-basins alone.
• The spatial gaps between basin boundaries offer a real-space interpretation of charge transfer and electron sharing.
• The proposed regularity accurately reflects the nature of chemical bonds based on electron sharing.