Self-Attractive Hartree Decomposition: Partitioning Electron Density into Smooth Localized Fragments

Area of Science:

• Quantum Chemistry
• Computational Chemistry
• Chemical Physics

Background:

• Chemical bonding is fundamental to chemistry.
• Current methods often rely on molecular orbitals from quantum chemical calculations.
• Molecular orbitals are not directly experimentally observable.

Purpose of the Study:

• To present a new method, self-attractive Hartree (SAH) decomposition.
• To analyze electron pairs directly from electron density.
• To provide an experimentally accessible alternative to molecular orbital methods.

Main Methods:

• Partitioning electron density into one-electron fragments.
• Maximizing self-repulsion and maintaining regular fragment shapes.
• Solving novel equations with self-attractive Hartree potentials.

Main Results:

• SAH decomposition reveals symmetry breaking and localization consistent with chemical intuition.
• The method effectively visualizes single/multiple bonds, lone pairs, and unusual bonds.
• SAH decomposition accurately models hydrogen bonding and identifies bonds in molecular complexes.

Conclusions:

• SAH decomposition offers a powerful, experimentally grounded approach to chemical bonding analysis.
• The method provides chemically intuitive insights into electron distribution.
• It serves as a valuable tool for visualizing and understanding various bonding phenomena.