Basis-set correction based on density-functional theory: Linear-response formalism for excited-state energies

Area of Science:

• Quantum Chemistry
• Computational Physics

Background:

• Basis-set correction methods improve ground-state energy calculations by incorporating missing electron correlation effects.
• These methods accelerate convergence to the complete-basis-set limit.

Purpose of the Study:

• Extend the basis-set correction method to calculate excited-state energies using linear-response formalism.
• Investigate the impact of this extended method on the convergence of excitation and total energies.

Main Methods:

• Developed general linear-response equations for basis-set corrected excited-state calculations.
• Applied the method to a one-dimensional two-electron model system using configuration-interaction wave functions.
• Utilized a local-density-approximation functional for basis-set correction.

Main Results:

• The extended method did not accelerate the basis convergence of excitation energies.
• Significantly accelerated the basis convergence of excited-state total energies for the model system.

Conclusions:

• The basis-set correction method shows promise for improving the efficiency of excited-state total energy calculations.
• Further research is needed to address the convergence of excitation energies.