Fast and reliable ab initio calculation of crystal field splittings in lanthanide complexes.

Ab initio calculations of crystal field splittings and magnetic properties of lanthanide complexes are usually performed using state-averaged complete active space self-consistent field (CASSCF) calculations and a subsequent spin-orbit calculation mixing the CASSCF wave functions (CASSCF/state interaction with spin-orbit coupling). Because this approach becomes very time-consuming for large molecules, simplifications have been proposed in the literature to determine the state-averaged orbitals by configuration-averaged Hartree-Fock (CAHF) instead of CASSCF. We present an approach which is an extension of the CAHF method. We combine the techniques of local density fitting with CAHF and achieve a significant speedup compared to CASSCF without loss in accuracy. To assess the performance of our method, we apply it to three well-known molecules, namely, Er[N(SiMe3)2]3, Er(trensal), and the double-decker (NBu4)+ [Er(Pc)2]-.