Density Functional Theory for Microwave Spectroscopy of Noncovalent Complexes: A Benchmark Study

Area of Science:

• Computational Chemistry
• Quantum Chemistry
• Materials Science

Background:

• Accurate prediction of noncovalent interactions is crucial for understanding molecular behavior.
• Weakly bound complexes play vital roles in chemistry and biology.
• Evaluating computational methods for geometric predictions is essential.

Purpose of the Study:

• To compare the performance of 89 computational methods for predicting noncovalent bond lengths.
• To assess methods for noncovalent interaction energies and covalent bond lengths.
• To identify the most accurate density functionals and computational approaches.

Main Methods:

• Systematic evaluation of 89 computational methods.
• Benchmarking against established datasets for noncovalent and covalent bond lengths.
• Analysis of density functional approximations and dispersion corrections.

Main Results:

• The ωB97M-V method showed the best overall performance, achieving balanced results.
• B97M-V, B3LYP-D3(BJ), and DSD-PBEPBE-D3(BJ) were identified as top methods for noncovalent geometries.
• The study discussed the impact of density functional improvements and dispersion corrections.

Conclusions:

• ωB97M-V is a highly recommended method for predicting noncovalent bond lengths and interaction energies.
• Specific DFT functionals offer excellent accuracy for noncovalent geometry predictions.
• Understanding the effects of approximations aids in selecting appropriate computational tools.