Improved Gaussian basis sets for norm-conserving 4f-in-core pseudopotentials of trivalent lanthanides (Ln = Ce–Lu).

This article focuses on the development and optimization of atom-centered Gaussian basis sets, named LnBS2*, tailored for condensed-phase simulations of trivalent lanthanide systems using scalar-relativistic 4f-in-core norm-conserving Goedecker–Teter–Hutter (GTH) pseudopotentials (PPs). The authors introduce a unified, self-consistent optimization approach that simultaneously considers total energy, relative energy, condition number of the overlap matrix, and atomic orbital occupation to improve accuracy, transferability, and numerical stability over previous basis sets (LnBS2). Benchmarking against molecular and condensed-phase lanthanide systems—including lanthanide trihalides and aqueous solutions—demonstrates that LnBS2* basis sets yield lower total and relative energies, maintain reasonable condition numbers to avoid linear dependency issues, and reproduce structural and physical properties consistent with experimental and all-electron reference data. These optimized basis sets facilitate large-scale first-principles and ab initio molecular dynamics simulations of structurally complex lanthanide-containing materials.