Gaussian-type function set without prolapse 1H through 83Bi for the Dirac-Fock-Roothaan equation

Area of Science:

• Computational Chemistry
• Quantum Chemistry
• Atomic Physics

Background:

• Gaussian basis sets are crucial for atomic electronic structure calculations.
• Ensuring accuracy in relativistic quantum chemistry, especially for heavy elements, remains a challenge.
• Monotonic convergence of total energy is a key indicator of basis set quality.

Purpose of the Study:

• To develop novel, prolapse-free Gaussian basis sets for atomic calculations from Hydrogen (1H) to Bismuth (83Bi).
• To impose a monotonic decrease in Dirac-Fock-Roothaan (DFR) total energy towards the numerical DFR (NDF) limit.
• To achieve high accuracy in total energy calculations for heavy elements.

Main Methods:

• Development of even-tempered Gaussian basis sets.
• Imposition of monotonic energy convergence criteria in the Dirac-Fock-Roothaan (DFR) method.
• Systematic testing of basis sets for atoms up to Bismuth (83Bi).

Main Results:

• Developed prolapse-free Gaussian basis sets applicable to elements 1H-83Bi.
• Achieved high accuracy with |TE(DFR) - TE(NDF)| < or = 1 x 10(-6) hartree for atoms up to Bi.
• Proposed a practical basis set with |TE(DFR) - TE(NDF)| < or = 4 x 10(-5).

Conclusions:

• The developed Gaussian basis sets provide accurate and reliable total energies for heavy elements.
• These sets mitigate the issue of prolapse in atomic electronic structure calculations.
• The new basis sets are valuable tools for advanced computational chemistry research.