An analytical approach for calculating transfer integrals in superexchange coupled dimers

TL;DR

This paper derives an analytical expression for transfer integrals in superexchange-coupled dimers, linking molecular structure to magnetic properties, and validates it against numerical calculations, offering a new tool for understanding magnetic interactions.

Contribution

It introduces a novel analytical method to calculate transfer integrals in superexchange-coupled dimers, explicitly considering orbital interactions and molecular geometry.

Findings

Analytical expression accurately predicts transfer integrals.

Method validated against numerical electronic structure calculations.

Provides insights into magneto-structural correlations.

Abstract

An analytical expression for the transfer integral HAB between the localized magnetic orbitals in superexchange-coupled dimers as a function of the type of atoms and geometry of the molecule has been derived by explicitly including orbital interactions. It is shown that HAB plays the key role for the magnetic coupling constant J in understanding magneto-structural correlations. The reliability and capability of this approach is confirmed by comparison with numerical electronic structure calculations in the local spin-density approximation on singly and doubly bridged Cu(II)-dimers with fluorine ligands. All results can be calculated and understood within the analytical formalism representing, therefore, a powerful tool for understanding the magneto-structural correlations and also for constructing magnetic orbitals analytically.