Relativistic quintuple-zeta basis sets for the s block

Area of Science:

• Computational chemistry
• Quantum chemistry
• Relativistic quantum mechanics

Background:

• Accurate calculations for heavy elements are crucial in chemistry and physics.
• Existing basis sets may not fully capture relativistic effects and electron correlation for heavy systems.
• The development of high-quality basis sets is essential for advancing computational modeling.

Purpose of the Study:

• To present new relativistic basis sets of quintuple-zeta quality for s-block elements.
• To optimize basis sets for accurate treatment of valence and core electrons, including diffuse functions.
• To benchmark the performance of these basis sets for atomic and molecular properties.

Main Methods:

• Development of relativistic basis sets with quintuple-zeta quality.
• Optimization of self-consistent field exponents and correlating functions.
• Utilizing multireference singles and doubles configuration interaction calculations.
• Inclusion of diffuse functions for anions and related elements.

Main Results:

• New quintuple-zeta relativistic basis sets were generated for s-block elements.
• Basis sets showed smooth convergence towards the basis set limit with increasing quality.
• Benchmarking demonstrated reliable performance for atomic and molecular properties.
• The developed basis sets facilitate higher accuracy in heavy element calculations.

Conclusions:

• The new quintuple-zeta basis sets represent a significant advancement for relativistic quantum chemistry.
• These basis sets, combined with advanced computational methods, reduce uncertainty in calculations on heavy atoms and molecules.
• The availability of these basis sets will aid researchers in achieving unprecedented accuracy in computational studies.