The accurate calculation of dipole moments and dipole polarizabilities using Gaussian‐based density functional methods

Abstract Dipole moments and static dipole polarizabilities have been calculated for a number of small molecules using the linear combination of Gaussian‐type orbitals–local spin density method. The effect of augmenting standard orbital basis sets with polarization functions has been investigated. A set of optimum ζ d , for use in calculating polarizabilities, has been derived for the first‐row atoms C, N, O, and F. The results of this optimized doubly polarized double‐zeta basis set compare well with results obtained using a double‐zeta basis set augmented by four even‐tempered ζ d polarization functions. The results of the optimized basis set, and a basis set augmented with only a single ζ d polarization function derived from it, compare very favorably with those obtained from Møller–Plesset perturbation theory and with experimental data. They show a marked improvement on results obtained using standard Hartree–Fock self‐consistent‐field molecular orbital methods where no treatment of electron‐correlation is included.