B97-3c: A revised low-cost variant of the B97-D density functional method

Area of Science:

• Quantum Chemistry
• Computational Chemistry

Background:

• Established density functional approximations often struggle with large systems and accurately describing chemical properties.
• The B97-D functional provided a basis for improved approximations, but further refinement was needed for broad applicability.

Purpose of the Study:

• To propose a revised density functional approximation, B97-3c, for general applicability to chemical properties of large systems.
• To enhance accuracy in predicting molecular geometries, thermochemistry, kinetics, and non-covalent interactions.

Main Methods:

• Developed B97-3c based on Becke's 1997 power-series ansatz with D3 dispersion correction.
• Utilized a modified valence triple-zeta Gaussian basis set for elements up to Radon.
• Incorporated an atom-pairwise short-range potential to correct for bond length errors.

Main Results:

• B97-3c demonstrated excellent molecular and condensed phase geometries, comparable to hybrid functionals.
• Achieved good performance on the GMTKN55 database for thermochemistry, kinetics, and non-covalent interactions.
• Showed applicability to metal-organic reactions and suitability for systems with hundreds of atoms.

Conclusions:

• B97-3c is a robust, low-cost electronic structure method suitable for large systems.
• It offers a physically sound and asymptotically correct description of interactions, free from basis set superposition error.
• Recommended as a computational tool, especially for strongly correlated systems.