Development and Application of a Complete Active Space Spin-Orbit Configuration Interaction Program Designed for Single Molecule Magnets

Abstract

We present a spin-orbit configuration interaction program which has been tailored for the description of the magnetic properties of polynuclear metal complexes with partially filled d- and f-shells. The spin-orbit operators are directly included in the configuration interaction program based on Slater-determinants. The lowest states are obtained by a Block-Davidson-type diagonalisation. The usage of localised active orbitals enables the construction of start vectors from tensor products of single-center wave functions that already include spin-orbit interaction. This allows for an analysis of the role and the interplay of the different metal centres. Furthermore, in case of weak coupling of the metal centres these tensor products are already close to the final wave functions ensuring fast convergence. In combination with a two-layer hybrid parallelisation, this makes the program highly efficient. Based on the spin-orbit coupled wave functions, magnetic D-tensors, g-tensors and temperature-dependent susceptibilities can be calculated. The applicability and performance of the program is shown exemplarily on a trinuclear transition metal (CoIIVIICoII) complex.