All-Electron Scalar Relativistic Basis Sets for the Lanthanides

Area of Science:

• Computational chemistry
• Quantum chemistry
• Relativistic effects

Background:

• Lanthanide complexes require accurate computational methods.
• Existing basis sets may lack efficiency or accuracy for lanthanides.
• Relativistic effects are crucial for heavy elements like lanthanides.

Purpose of the Study:

• To develop and optimize Segmented All-Electron Relativistically Contracted (SARC) basis sets for lanthanides (La-Lu).
• To enable efficient and accurate density functional theory (DFT) calculations for lanthanide systems.
• To provide basis sets compatible with DKH2 and ZORA relativistic Hamiltonians.

Main Methods:

• Construction and optimization of SARC basis sets for La-Lu elements.
• Application of SARC basis sets with DKH2 and ZORA scalar relativistic Hamiltonians.
• Evaluation using DFT calculations of lanthanide ionization energies and trihalides.

Main Results:

• SARC basis sets accurately reproduce experimental ionization energy trends for lanthanides.
• Basis sets demonstrate balanced treatment of electronic configurations.
• Consistent, efficient, and reliable performance in molecular systems (lanthanide trihalides).

Conclusions:

• Optimized SARC basis sets offer significant computational advantages over generally contracted sets.
• Compact SARC basis sets can replace effective core potentials for routine lanthanide studies.
• These basis sets are valuable for molecular property calculations requiring explicit core electron treatment.