The effect of correlation on molecular magnetizabilities and rotational g tensors

Abstract

Using multiconfigurational self-consistent field (MCSCF) wave functions and perturbation-dependent basis sets, the effect of electron correlation on molecular magnetizabilities and rotational g tensors is investigated. The eight molecular systems considered (H2O, NH3, HF, C2H2, CO, H2CO, O3, and LiH) vary in the importance and relative magnitudes of the static and dynamic correlation contributions. The results for O3 are the first correlated calculations of the rotational g tensor of this system. We confirm previous findings that, except for systems with large static correlation effects, the effect of correlation on molecular magnetizabilities is small. A somewhat larger correlation contribution is usually observed for the rotational g tensor, although this property is also rather insensitive to the correlation treatment. Agreement with experimental rotational g tensors is only fair and estimates of rovibrational corrections are needed to assess properly the accuracy of theoretically calculated rotational g tensors.