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Norm-Conserving Pseudopotentials and Basis Sets To Explore Lanthanide Chemistry in Complex Environments
journal contribution
posted on 2019-10-17, 13:41 authored by Jun-Bo Lu, David C. Cantu, Manh-Thuong Nguyen, Jun Li, Vassiliki-Alexandra Glezakou, Roger RousseauA complete
set of pseudopotentials and accompanying basis sets
for all lanthanide elements are presented based on the relativistic,
norm-conserving, separable, dual-space Gaussian-type pseudopotential
protocol of Goedecker, Teter, and Hutter (GTH) within the generalized
gradient approximation (GGA) and the exchange–correlation functional
of Perdew, Burke, and Ernzerhof (PBE). The corresponding basis sets
have been molecularly optimized (MOLOPT) using a contracted form with
a single set of Gaussian exponents for the s, p, and d states. The
f states are uncontracted explicitly with Gaussian exponents. Moreover,
the Hubbard U values for each lanthanide element,
for DFT+U calculations, are also tabulated, allowing
for the proper treatment of the strong on-site Coulomb interactions
of localized 4f electrons. The accuracy and reliability of our GTH
pseudopotentials and companion basis sets optimized for lanthanides
is illustrated by a series of test calculations on lanthanide-centered
molecules, and solid-state systems, with the most common oxidation
states. We anticipate that these pseudopotentials and basis sets will
enable larger-scale density functional theory calculations and ab
initio molecular dynamics simulations of lanthanide molecules in either
gas or condensed phases, as well as of solid state lanthanide-containing
materials, allowing further exploration of the chemical and physical
properties of lanthanide systems.