Property-Optimized Gaussian Basis Sets for Lanthanides

09 September 2021, Version 2
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Property-optimized Gaussian basis sets of split-valence, triple-zeta and quadruple-zeta valence quality are developed for the lanthanides Ce–Lu for use with small-core relativistic effective core potentials. They are constructed in a systematic fashion by augmenting def2 orbital basis sets with diffuse basis functions and minimizing negative static isotropic polarizabilities of lanthanide atoms with respect to basis set exponents within the unrestricted Hartree–Fock method. The basis set quality is assessed using a test set of 70 molecules containing the lanthanides in their common oxidation states and f electron occupations. 5d orbital occupation turns out to be the determining factor for the basis set convergence of polarizabilities in lanthanide atoms and the molecular test set. Therefore, two series of property-optimized basis sets are defined. The augmented def2-SVPD, def2-TZVPPD, and def2-QZVPPD basis sets balance the accuracy of polarizabilities across lanthanide oxidation states. The relative errors in atomic and molecular polarizability calculations are ≤8% for augmented split-valence basis sets, ≤2.5% for augmented triple-zeta valence basis sets, and ≤1% for augmented quadruple-zeta valence basis sets. In addition, extended def2-TZVPPDD and def2-QZVPPDD are provided for accurate calculations of lanthanide atoms and neutral clusters. The property-optimized basis sets developed in this work are shown to accurately reproduce electronic absorption spectra of a series of LnCp'3- complexes (Cp' = C5H4SiMe3, Ln = Ce–Nd, Sm) with time-dependent density functional theory.

Keywords

Density functional theory
Gaussian basis sets
Molecular properties
Optical absorption
Lanthanides

Supplementary materials

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Title
Supplementary Material for Property-Optimized Gaussian Basis Sets for Lanthanides
Description
Supplementary material contains unrestricted Hartree–Fock energies and static isotropic polarizabilities of lanthanide atoms and the molecular test set, Cartesian coordinates of the molecular test set, and electronic excitations in LnCp'3- complexes (Cp' = C5H4SiMe3, Ln = Ce–Nd, Sm).
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