Density-Corrected Density Functional Theory for Molecular Properties.

Area of Science:

• Quantum Chemistry
• Computational Materials Science
• Theoretical Chemistry

Background:

• Self-interaction error (SIE) is a known limitation in density functional theory (DFT).
• Density-corrected DFT (DC-DFT) offers a potential solution by incorporating Hartree-Fock electron density non-self-consistently.
• Previous evaluations of DC-DFT primarily focused on total energy differences.

Purpose of the Study:

• To systematically evaluate the performance of DC-DFT for molecular properties beyond total energies.
• To assess DC-DFT's accuracy for dipole moments, static polarizabilities, and electric field gradients (EFGs).
• To compare DC-DFT results with accurate coupled-cluster reference data.

Main Methods:

• Implementation of the density-corrected DFT (DC-DFT) procedure.
• Generation of high-accuracy reference data using coupled-cluster theory.
• Calculation and comparison of molecular properties (dipole moments, polarizabilities, EFGs) using both DC-DFT and standard self-consistent DFT.

Main Results:

• DC-DFT generally performs well for electric field gradients (EFGs), including challenging cases like CuCl.
• DC-DFT shows no detrimental effect on dipole moment calculations.
• A negative impact of DC-DFT on polarizability was observed in at least one molecular case.

Conclusions:

• DC-DFT is a viable method for calculating electric field gradients with high accuracy.
• The performance of DC-DFT for polarizability calculations may require further refinement.
• This study provides a systematic assessment of DC-DFT for various molecular properties, guiding future applications.