Gaussian basis sets for use in correlated molecular calculations. IV. Calculation of static electrical response properties

TLDR

An accurate description of atomic and molecular electrical properties is essential for quantitative predictions of nonlinear behavior and long‑range interactions between neutral and charged species. The authors systematically investigate the basis sets needed to obtain accurate correlated values for the static dipole, quadrupole, octopole polarizabilities, and hyperpolarizability of He, Ne, and Ar. They evaluate multiple correlation methods—MP2, MP3, MP4, CCSD, CCSD(T), and CISD—using even‑tempered diffuse extensions of Dunning’s correlation‑consistent basis sets, and apply these to rare‑gas atoms as well as selected anions and molecules to test basis‑set performance. Multiply‑augmented basis sets produce static electrical properties for the rare gases that converge smoothly and agree excellently with experimental and previously computed results.

Abstract

An accurate description of the electrical properties of atoms and molecules is critical for quantitative predictions of the nonlinear properties of molecules and of long-range atomic and molecular interactions between both neutral and charged species. We report a systematic study of the basis sets required to obtain accurate correlated values for the static dipole (α1), quadrupole (α2), and octopole (α3) polarizabilities and the hyperpolarizability (γ) of the rare gas atoms He, Ne, and Ar. Several methods of correlation treatment were examined, including various orders of Moller–Plesset perturbation theory (MP2, MP3, MP4), coupled-cluster theory with and without perturbative treatment of triple excitations [CCSD, CCSD(T)], and singles and doubles configuration interaction (CISD). All of the basis sets considered here were constructed by adding even-tempered sets of diffuse functions to the correlation consistent basis sets of Dunning and co-workers. With multiply-augmented sets we find that the electrical properties of the rare gas atoms converge smoothly to values that are in excellent agreement with the available experimental data and/or previously computed results. As a further test of the basis sets presented here, the dipole polarizabilities of the F− and Cl− anions and of the HCl and N2 molecules are also reported.