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

Journal Article · · Journal of Chemical Physics; (United States)
DOI:https://doi.org/10.1063/1.466439· OSTI ID:5316859
;  [1]
  1. Molecular Science Research Center, Pacific Northwest Laboratory, P.O. Box 999, Richland, Washington 99352 (United States)

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 ([alpha][sub 1]), quadrupole ([alpha][sub 2]), and octopole ([alpha][sub 3]) polarizabilities and the hyperpolarizability ([gamma]) 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[sup [minus]] and Cl[sup [minus]] anions and of the HCl and N[sub 2] molecules are also reported.

DOE Contract Number:
AC06-76RL01830; FG06-89ER75522
OSTI ID:
5316859
Journal Information:
Journal of Chemical Physics; (United States), Vol. 100:4; ISSN 0021-9606
Country of Publication:
United States
Language:
English