How Large is the Elephant in the Density Functional Theory Room?

Area of Science:

• Computational Chemistry
• Quantum Chemistry

Background:

• A recent study questioned the accuracy of Gaussian basis sets in density functional theory (DFT) for calculating atomization energies and dipole moments.
• The study reported high accuracy with a multiwavelet-based method, suggesting limitations of standard Gaussian basis sets like aug-cc-pVXZ.

Purpose of the Study:

• To investigate if Gaussian basis sets, when optimized for DFT, can achieve accuracy comparable to advanced multiwavelet methods.
• To re-evaluate the suitability of Gaussian basis sets for high-accuracy computational chemistry.

Main Methods:

• Utilized Gaussian basis sets specifically optimized for density functional theory calculations.
• Compared the accuracy of these optimized Gaussian basis sets against results from a multiwavelet-based approach for atomization energies and dipole moments.

Main Results:

• Gaussian basis sets optimized for DFT demonstrated accuracy comparable to the multiwavelet approach.
• This indicates that Gaussian basis sets are capable of achieving high accuracy in DFT calculations when properly chosen.

Conclusions:

• Gaussian basis sets, when optimized for DFT, are suitable for achieving high accuracy in computational chemistry.
• The previous limitations observed with standard Gaussian sets may be overcome through targeted optimization for specific theoretical methods.