Abstract
The reliability of the small-core lanthanide effective core potentials (ECP) is tested using MF and MF\(_3\), for M=Eu, Gd, Tb, and Yb and the atomic excitation energies for Pr, Nd, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb. In some case, the ECP and all-electron (AE) results are in good agreement, while in others there are significant differences. The differences are much larger when the segmented basis set is used in conjunction with the ECP than when the atomic natural orbital (ANO) basis set is used. The study of the atoms suggests that problems for lanthanide-containing molecules are associated with poor atomic excitation energies in the ECP treatment and even using the ANO basis set does not completely solve the problem. We note that the problem appears to be more severe for density functional approaches than for traditional correlation methods. We suggest that additional studies and new effective core potentials may be required for the lanthanide atoms.
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Funding
This work was supported by NASA’s Transformative Aeronautics Concepts Program as a part of the Transformative Tools and Technologies Project. Resources supporting this work were provided by the NASA High-End Computing (HEC) Program through the NASA Advanced Supercomputing (NAS) Division at Ames Research Center.
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Bauschlicher, C.W. The reliability of the small-core lanthanide effective core potentials. Theor Chem Acc 141, 11 (2022). https://doi.org/10.1007/s00214-022-02867-9
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DOI: https://doi.org/10.1007/s00214-022-02867-9