Calculation of the zero-field splitting tensor on the basis of hybrid density functional and Hartree-Fock theory.

The zero-field splitting (ZFS) (expressed in terms of the D tensor) is the leading spin-Hamiltonian parameter for systems with a ground state spin S>12. To first order in perturbation theory, the ZFS arises from the direct spin-spin dipole-dipole interaction. To second order, contributions arise from spin-orbit coupling (SOC). The latter contributions are difficult to treat since the SOC mixes states of different multiplicities. This is an aspect of dominant importance for the correct prediction of the D tensor. In this work, the theory of the D tensor is discussed from the point of view of analytic derivative theory. Starting from a general earlier perturbation treatment [F. Neese and E. I. Soloman, Inorg. Chem. 37, 6568 (1998)], straightforward response equations are derived that are readily transferred to the self-consistent field (SCF) Hartree-Fock (HF) or density functional theory (DFT) framework. The main additional effort in such calculations arises from the solution of nine sets of nonstandard coupled-perturbed SCF equations. These equations have been implemented together with the spin-orbit mean-field representation of the SOC operator and a mean-field treatment of the direct spin-spin interaction into the ORCA electronic structure program. A series of test calculations on diatomic molecules with accurately known zero-field splittings shows that the new approach corrects most of the shortcomings of previous DFT based methods and, on average, leads to predictions within 10% of the experimental values. The slope of the correlation line is essentially unity for the B3LYP and BLYP functionals compared to approximately 0.5 in previous treatments.