Dispersion-Corrected Mean-Field Electronic Structure Methods.

Area of Science:

• Computational Chemistry
• Quantum Chemistry
• Materials Science

Background:

• Standard electronic structure methods (e.g., Hartree-Fock, DFT) neglect long-range electron correlation (London dispersion).
• Accurate modeling of large chemical systems and intramolecular phenomena necessitates inclusion of dispersion forces.

Purpose of the Study:

• To review recent advancements in dispersion correction methods for electronic structure calculations.
• To provide a critical assessment of methods suitable for routine, large-scale applications.

Main Methods:

• Classification of dispersion correction schemes into three groups: nonlocal density-based, semiclassical C6-based, and one-electron effective potentials.
• Critical discussion of the properties, advantages, and disadvantages of each method.
• Presentation of benchmarks on molecular complexes and crystals.

Main Results:

• Dispersion corrections significantly improve the accuracy of electronic structure calculations for large systems.
• Various methods achieve typical relative errors of 5% for long-range dispersion energies.
• The accuracy of dispersion-corrected methods often surpasses that of the underlying mean-field theory.

Conclusions:

• Dispersion corrections are essential for realistic computational chemistry, particularly for condensed matter and complex molecules.
• Current methods offer a clear improvement in accuracy, though areas like robustness and short-range effects require further development.
• The reviewed approaches provide reliable long-range dispersion energies, crucial for thermochemistry and molecular interactions.