La-Luの元素に対する大コアECPのエラー整合性基底関数系

We present the extension of the system of error-consistent segmented contracted Gaussian basis sets (Karlsruhe def2-bases [Weigend and Ahlrichs, Phys. Chem. Chem. Phys., 2005, 7, 3297-3305]) for the lanthanide large core effective core potentials (lcECPs) designed by Dolg, Stoll, Savin and Preuss, Theor. Chim. Acta, 1989, 75, 173-194. For La-Lu, sets of double zeta ("split", S), triple zeta (TZ), and quadruple zeta (QZ) valence (V) quality were optimized in atomic Hartree-Fock calculations for each of the different lcECPs that model the occupations f^n-k, k = 0, 1, 2, and n being the (typical) ground state f shell occupation; e.g. for Pr, n = 3, for each of the occupations f³, f², and f¹, an SV, TZV, and QZV basis were optimized and termed lcecp-k-XV (k = 0, 1, 2, X = S, TZ, QZ). Polarization functions for the quadruple zeta valence bases were taken from Weigand, Cao, Yang, and Dolg, Theor. Chem. Acc., 2010, 126, 117-127, for the smaller basis sets they were appropriately reduced. The conformity with the def2-series in regards to error-consistency was assessed for a set of 120 molecules by comparing distances, bond angles, vibration frequencies and exchange reaction energies in regards to the basis set limit and also to all-electron scalar relativistic calculations.