Norm-Conserving 4f-in-Core Pseudopotentials and Basis Sets Optimized for Trivalent Lanthanides (Ln = Ce-Lu)

Area of Science:

• Computational Chemistry
• Quantum Chemistry
• Materials Science

Background:

• Lanthanides (Ln) present unique challenges in electronic structure calculations due to their open 4f shell.
• Accurate modeling of lanthanide chemistry is crucial for applications in catalysis, materials science, and medicine.

Purpose of the Study:

• To develop and validate scalar-relativistic, 4f-in-core pseudopotentials and Gaussian basis sets for the entire lanthanide series (Ce-Lu).
• To provide an efficient and accurate computational approach for studying complex lanthanide systems.

Main Methods:

• Utilized the Goedecker, Teter, and Hutter (GTH) formalism with the Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA) functional.
• Constructed 4f-in-core pseudopotentials by including the 4f subconfiguration within the atomic core.
• Performed extensive computational benchmarks on various lanthanide systems, including molecular complexes, solutions, and solids.

Main Results:

• The developed 4f-in-core GTH pseudopotentials and basis sets accurately reproduce key features of lanthanide structural chemistry and reaction energetics, especially for nonredox reactions.
• Successfully modeled chemical bonding, solvation shells, hydrolysis, acidity, and solid-state properties of lanthanide systems.
• Demonstrated the efficiency of the 4f-in-core approach for complex systems and condensed-phase electronic structure calculations.

Conclusions:

• The new 4f-in-core GTH pseudopotentials offer a highly efficient and reliable method for studying lanthanide chemistry.
• This work facilitates multi-scale modeling of complex lanthanide-containing systems, including first-principles molecular dynamics simulations.
• Bridges the gap between localized 4f electron treatment and efficient pseudopotential formalisms for lanthanides.