Kohn-Sham self-interaction correction in real time.

Area of Science:

• Quantum Chemistry
• Computational Physics
• Electronic Structure Theory

Background:

• Standard time-dependent density functional theory (TD-DFT) methods often fail to accurately describe electronic excitations, particularly charge-transfer excitations.
• Self-interaction error is a known limitation in common density functional approximations, impacting the accuracy of calculated electronic properties.

Purpose of the Study:

• To develop and present a novel solution scheme for time-dependent Kohn-Sham self-interaction correction (TD-LSIC).
• To accurately describe various electronic excitations, including charge-transfer excitations, using the developed TD-LSIC method.

Main Methods:

• The study employs the generalized optimized effective potential (OEP) approach.
• A multiplicative Kohn-Sham potential is constructed in real time and real space for the self-interaction corrected local density approximation (SIC-LDA).

Main Results:

• The developed TD-LSIC approach correctly describes electronic excitations of different characters.
• Charge-transfer excitations, previously a benchmark for TD-DFT failures, are accurately reproduced.
• Analysis of the time-dependent exchange-correlation potential and density reveals key features responsible for the improved description of electronic response.

Conclusions:

• The presented TD-LSIC scheme offers a significant advancement in accurately calculating electronic excitations.
• This method overcomes limitations of standard TD-DFT, providing a reliable tool for studying complex electronic phenomena.