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

TL;DR

This paper presents a theoretical framework combining molecular orbital theory and multi-configurational self-consistent field methods to analyze magnetic properties of molecular magnets, demonstrated on Ni4Mo12 and a spin-one dimer.

Contribution

It introduces a structured approach for modeling magnetic spectra using a post-Hartree-Fock scheme and bilinear spin Hamiltonians, applicable to transition metal and rare earth magnetic units.

Findings

Successfully characterizes magnetic spectra of Ni4Mo12

Derives explicit eigenenergies for the spin Hamiltonian

Demonstrates method efficiency on a spin-one dimer

Abstract

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 Ni$_4$Mo$_{12}$. 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.