Construction of self-interaction-corrected exchange-correlation functionals within the correlation factor approach.

Area of Science:

• Quantum Chemistry
• Computational Physics
• Materials Science

Background:

• The accurate modeling of the exchange-correlation hole is crucial for the predictive power of Kohn-Sham density functional theory.
• Existing models often struggle with self-interaction errors, particularly in one-electron regions.
• The correlation factor ansatz offers a novel framework for constructing the exchange-correlation hole.

Purpose of the Study:

• To introduce a modified correlation factor model designed to mitigate self-interaction error.
• To develop a new exchange-correlation energy functional based on the self-interaction corrected hole.
• To implement and assess the performance of the new functional in molecular property calculations.

Main Methods:

• Utilizing a recently developed correlation factor ansatz for the exchange-correlation hole.
• Constructing a modified correlation factor that reduces to one in localized one-electron regions.
• Generating an exchange-correlation energy functional from the self-interaction corrected hole.
• Implementing the functional into a Kohn-Sham electronic structure code.

Main Results:

• The modified correlation factor successfully reduces self-interaction error.
• The new exchange-correlation functional shows improved performance.
• Calculations of various molecular properties demonstrate significant advancements over previous models.
• The approach yields more accurate predictions for electronic structure.

Conclusions:

• The developed correlation factor model represents a significant improvement for Kohn-Sham theory.
• The method effectively addresses the long-standing issue of self-interaction error.
• This work provides a more robust and accurate tool for computational chemistry and physics.