Perturbative total energy evaluation in self-consistent field iterations: tests on molecular systems

Area of Science:

• Quantum Chemistry
• Computational Physics

Background:

• The Hohenberg-Kohn-Sham (HKS) and Harris energy functionals are foundational in density functional theory.
• Accelerating self-consistent field (SCF) convergence is crucial for computational efficiency in quantum chemistry.

Purpose of the Study:

• To generalize the corrected HKS and Harris total energy functionals to the Hartree-Fock (HF) method.
• To evaluate the effectiveness of these generalized functionals in accelerating SCF convergence for molecular systems.

Main Methods:

• Generalization of previously proposed corrected HKS and Harris energy functionals.
• Application and testing of the generalized functionals on selected molecular systems within the HF framework.

Main Results:

• The generalized energy functionals were successfully incorporated into the Hartree-Fock method.
• Testing demonstrated that the functionals significantly accelerate the convergence of the total energy during the SCF process.

Conclusions:

• The generalized corrected HKS and Harris energy functionals are effective tools for accelerating SCF convergence in Hartree-Fock calculations.
• These functionals offer a valuable method for improving the computational efficiency of quantum chemical simulations.