Self-interaction correction in a real-time Kohn-Sham scheme: access to difficult excitations in time-dependent...

Area of Science:

• Computational Chemistry
• Quantum Mechanics
• Materials Science

Background:

• Self-interaction error (SIC) is a significant issue in density functional theory (DFT) approximations.
• Accurate electronic structure calculations are crucial for understanding material and molecular properties.

Purpose of the Study:

• To develop and validate a real-time propagation scheme for self-interaction correction (SIC) within the Kohn-Sham framework.
• To investigate the behavior of the time-dependent exchange-correlation potential in the presence of SIC.

Main Methods:

• Real-time and real-space construction of a multiplicative Kohn-Sham potential using the generalized optimized effective potential equation.
• Application to hydrogen-terminated silicon clusters, conjugated molecular chains, and molecular charge-transfer systems.
• Analysis of electronic excitations via transition densities and the time-dependent exchange-correlation potential.

Main Results:

• The real-time Kohn-Sham SIC scheme demonstrates promising accuracy across diverse test systems.
• A properly constructed Kohn-Sham SIC potential exhibits time-dependent field-counteracting behavior.
• Approximations like the SIC-Slater potential may not preserve these essential characteristics.

Conclusions:

• The developed real-time propagation scheme offers a robust method for incorporating self-interaction correction.
• This approach provides a more accurate description of electronic excitations and potential behavior.
• Highlights the importance of the specific construction of the exchange-correlation potential for accurate results.