All-electron scalar relativistic basis sets for the elements Rb-Xe.

Area of Science:

• Quantum Chemistry
• Computational Chemistry
• Atomic and Molecular Physics

Background:

• Relativistic effects are crucial for accurate electronic structure calculations of heavy elements.
• Existing basis sets may not be optimally suited for specific scalar relativistic Hamiltonians.
• Efficient basis sets are needed for routine calculations on large molecular systems.

Purpose of the Study:

• To develop and present Segmented all-electron relativistically contracted (SARC) basis sets for elements 37 Rb to 54 Xe.
• To optimize these basis sets for use with scalar relativistic methods like the Douglas-Kroll-Hess approach and the zeroth-order regular approximation.
• To provide basis sets suitable for both density functional theory and correlated wave function theory.

Main Methods:

• Generation of a common set of exponents using established heuristic procedures.
• Individual optimization of contractions for each scalar relativistic Hamiltonian.
• Assessment of basis set quality against large decontracted reference sets.
• Validation through calculations on atomic, ionic, and molecular properties.

Main Results:

• Development of triple-zeta quality SARC basis sets for Rb-Xe.
• Basis sets feature compact size and loose segmented contractions.
• Singly and doubly polarized versions are available.
• Optimized contractions enhance suitability for specific scalar relativistic Hamiltonians.

Conclusions:

• The presented SARC basis sets offer an efficient and accurate choice for relativistic calculations involving elements Rb-Xe.
• Their design facilitates routine computations on large systems and studies of core spectroscopic properties.
• The basis sets are versatile, applicable to both DFT and correlated wave function methods.