The resolution of the identity approximation for calculations of spin-spin contribution to zero-field splitting parameters

Abstract

In this work, the resolution of the identity (RI) approximation is developed for the calculation of the electron-electron spin-spin coupling (SSC) interaction that is a central component of the zero-field splitting (ZFS) term in the effective spin Hamiltonian. The approximated integrals are then used in large-scale multireference configuration interaction treatments of the SSC interaction. The SSC contribution to the ZFS is treated using the Breit–Pauli spin-spin Hamiltonian in conjunction with first-order perturbation theory. Test calculations on a set of diatomic molecules reveal that the error of the RI approximation does not exceed 0.01 cm−1 even if standard auxiliary basis sets are used. This error of less than 1% is considered to be negligible compared to the presently achievable accuracy of the SSC calculations relative to experimental data. The present development allows the correlated ab initio calculation of ZFS parameters of larger systems such as linear polyenes and linear polyacenes. The basis set convergence of the calculated ZFS values was investigated, and the effect of electronic correlation on the calculated ZFS parameters is discussed.