Rational Design of atomic Gaussian basis sets for Ab initio Calculations of the dipole polarizabilities and hyperpolarizabilities II. Moderate Size Basis 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 design rules, elaborated earlier in the first paper of this series for the construction of atomic Gaussian basis sets, tailored for the calculations of molecular polarizabilities αij and hyperpolarizabilities βijk at the SCF level, are tested here by the example of the basis set families, generated from the energy-optimized (9s5p) parent set. Adding the polarization sets to contracted sp substrates of various flexibility, we generate the [4s3pNdMf], [5s3pNdMf] and [6s4pNdMf] bases families, which are combined with the corresponding [3sNpMd] and [4sNpMd] bases for Hydrogen. The SCF results for H2CO, CH3CN, and HCN molecules, obtained with (11s7p3d/6s3p)/[6s4p3d/4s3p], are used as a benchmark here. The contraction flexibility is shown to affect the convergence of both αij and βijk values only insignificantly, slightly increasing the uncertainties of the calculated data. The smallest [4s3p3d/3s3p] basis is recommended for the calculation of (hyper)polarizabilities of large molecules within the SCF approximation. For the conjugated organic molecules with dominant ÏĂ-electron polarization rather reliable SCF results are obtained at the [4s3p2d/3s] level. So, for p-nitroaniline this basis set reproduces the results obtained with [6s4p3d/4s3p] basis with the error 1% for αij and 3% for dominant longitudinal hyperpolarizability βzzz.
Keywords: gaussian basis sets, convergence, SCF calculations of electric properties, polarizability and hyperpolarizability
