Rational Design of atomic gaussian basis sets for Ab initio calculations of the dipole polarizabilities and hyperpolarizabilities. I. Optimized polarization sets for the first-row atoms from B to F
Issue title: Computational aspects of electric polarizability calculations: Atoms, Molecules and clusters, Part I
Affiliations: A.E. Arbuzov Institute of Organic and Physical Chemistry of Kazan Scientific Centre, Russian Academy of Sciences, Arbuzov str., 8, 420088, Kazan, Russia
Abstract: The rational design rules for atomic Gaussian basis sets, tailored for the calculations of molecular polarizabilities αij and hyperpolarizabilities βijk at the SCF level, are elaborated. The sequence of the optimized polarization sets (2d), (3d), (4d), (3d1f), (4d3f) for the first-row atoms from B to F is constructed, the optimization technique is supposed to provide a rapid convergence of both αij and βijk with the size of the polarization set. Adding of these polarization sets to the [6s4p] and [6s5p] substrates, derived from the energy-optimized (10s6p) primitive set of Huzinaga, gives the [6s4pNdMf] and [6s5pNdMf] bases families. They are combined with the corresponding [4sNpMd] and [5sNpMd] bases for Hydrogen built up in the same manner. The convergence of SCF results with the size of the basis set has been thoroughly investigated by the examples of H2CO, CH3CN, and HCN molecules. It has been established that both αij and βijk values converge to their saturation limits at the [6s4p3d/4s3p] level. This basis set provides the results, which are very close to near HF limit values, estimated with the most sophisticated polarized Gaussian basis sets used up to now.
Keywords: gaussian basis sets, convergence, SCF calculations of electric properties, polarizability and hyperpolarizability
