Molecular magnetism in the multi-configurational self-consistent field method.

We develop a structured theoretical framework used in our recent articles Eur. Phys. J. B 92, 93 (2019) and Phys. Rev. B 101, 094427 (2020) to characterize the unusual behavior of the magnetic spectrum, magnetization and magnetic susceptibility of the molecular magnet Ni4Mo12. The theoretical background is based on the molecular orbital theory in conjunction with the multi-configurational self-consistent field method and results in a post-Hartree-Fock scheme for constructing the corresponding energy spectrum. Furthermore, we construct a bilinear spin-like Hamiltonian involving discrete coupling parameters accounting for the relevant spectroscopic magnetic excitations, magnetization and magnetic susceptibility. The explicit expressions of the eigenenergies of the ensuing Hamiltonian are determined and the physical origin of broadening and splitting of experimentally observed peaks in the magnetic spectra is discussed. To demonstrate the efficiency of our method we compute the spectral properties of a spin-one magnetic dimer. The present approach may be applied to a variety of magnetic units based on transition metals and rare earth elements.