Property-optimized Gaussian basis sets for lanthanides

Property-optimized Gaussian basis sets of split-valence, triple-zeta valence, and quadruple-zeta valence quality are developed for the lanthanides Ce–Lu use with small-core relativistic effective core potentials. They constructed in a systematic fashion by augmenting def2 orbital diffuse functions minimizing negative static isotropic polarizabilities lanthanide atoms respect to set exponents within unrestricted Hartree–Fock method. The is assessed using test 70 molecules containing their common oxidation states f electron occupations. 5d occupation turns out be determining factor convergence molecular set. Therefore, two series property-optimized defined. augmented def2-SVPD, def2-TZVPPD, def2-QZVPPD balance accuracy across states. relative errors atomic polarizability calculations ≤8% split-valence sets, ≤ 2.5% ≤1% sets. In addition, extended def2-TZVPPDD def2-QZVPPDD provided accurate neutral clusters. this work shown accurately reproduce electronic absorption spectra LnCp3′− complexes (Cp′ = C5H4SiMe3, Ln Ce–Nd, Sm) time-dependent density functional theory.