ωB97X-3c: A composite range-separated hybrid DFT method with a molecule-optimized polarized valence double-ζ basis...

Area of Science:

• Computational Chemistry
• Quantum Chemistry
• Materials Science

Background:

• Density Functional Theory (DFT) is crucial for predicting molecular properties.
• Existing DFT methods face challenges in accuracy, computational cost, and describing specific interactions.
• The GMTKN55 database highlights the performance of various density functionals for thermochemistry.

Purpose of the Study:

• To introduce a new composite DFT method, ωB97X-3c, for improved accuracy and efficiency.
• To extend the family of "3c" methods for range-separated hybrid DFT.
• To provide a reliable DFT method applicable to all elements up to Radon (Z=1-86).

Main Methods:

• Development of a composite DFT method based on the ωB97X-V functional.
• Inclusion of a fully optimized polarized valence double-ζ (vDZP) Gaussian basis set.
• Utilization of large-core effective core potentials and a D4 dispersion correction.

Main Results:

• The vDZP basis set exhibits minimal basis set superposition errors (BSSEs), comparable to triple-ζ quality sets.
• The D4 damping scheme effectively mitigates residual BSSEs, removing the need for explicit corrections.
• ωB97X-3c demonstrates performance on par with or superior to standard hybrid DFT methods in quadruple-zeta basis sets.

Conclusions:

• The ωB97X-3c method provides a computationally inexpensive yet highly accurate approach for thermochemistry.
• It shows particular strengths in describing non-covalent interactions and reaction barrier heights.
• This method represents a significant advancement in efficient and reliable DFT calculations.