Design and application of a multicoefficient correlation method for dispersion interactions.

Area of Science:

• Computational chemistry
• Quantum mechanics
• Intermolecular forces

Background:

• Accurate calculation of van der Waals interactions is crucial for understanding molecular behavior.
• Existing methods can be computationally expensive or lack transferability.
• Rare gas interactions serve as fundamental benchmarks for developing new theoretical models.

Purpose of the Study:

• To introduce a novel multicoefficient correlation method (MCCM) for precise van der Waals interaction determination.
• To develop a transferable and computationally efficient model for dispersion interactions.
• To validate the MCCM's applicability to diverse systems beyond its parametrization set.

Main Methods:

• A new parametrization strategy fitting to high-level binding, Hartree-Fock, and correlation energies.
• Decomposition of energy into Hartree-Fock and correlation components for improved model transferability.
• Application to krypton dimer, rare gas-water interactions, and rare gas trimers (He3, Ne3, Ar3).

Main Results:

• The MCCM demonstrates high accuracy and transferability across various systems, including those not used in its parametrization.
• A high-level correction method for two-body interactions in rare gas trimers was developed.
• The MCCM significantly reduces computational cost for studying dispersion interactions in larger systems.

Conclusions:

• The MCCM provides a reliable and computationally efficient tool for accurate van der Waals interaction calculations.
• The method is transferable to systems like krypton dimer, rare gas-water, and rare gas trimers.
• MCCM offers a valuable resource for rare gas cluster studies, force field development, and semiempirical quantum models.