The magnetizability, rotational g tensor, and quadrupole moment of PF 3 revisited

Abstract

The Hartree-Fock limit is determined for the molecular dipole moment (μ), the molecular quadrupole moment ( Θ ∥, the magnetizability (ξ), and the rotational g tensor ( g) of PF 3. It is demonstrated that rotational London orbitals are crucial for obtaining reliable magnetic properties. Indeed, even with a basis set of augmented polarized triple-zeta quality, the signs of the rotational g tensor components are wrong when conventional basis functions are used. Using rotational London orbitals, the calculated components of the magnetizability tensor and the rotational g tensor agree with the experimentally observed quantities obtained from the doublet splittings of the rotational transitions, but not with the experimentally derived components of the g tensor nor with the experimental quadrupole moment. The Hartree-Fock limits of the different quantities are estimated to be: μ = 0.572±0.004 a.u., Θ ∥ = 0.690±0.010 a.u, g⊥ = −0.0643±0.0007, g ∥ = −0.0383± 0.0003, ξ = −6.61±0.06 a.u. and δξ = −0.33±0.02 a.u.