title: Improving the calculation of magnetic coupling constants in MRPT methods.
abstract: The magnetic coupling in transition metal compounds with more than one unpaired electron per magnetic center has been studied with multiconfigurational perturbation theory. The usual shortcomings of these methodologies (severe underestimation of the magnetic coupling) have been overcome by describing the Slater determinants with a set of molecular orbitals that maximally resemble the natural orbitals of a high-level multiconfigurational reference configuration interaction calculation. These orbitals have significant delocalization tails onto the bridging ligands and largely increase the coupling strengths in the perturbative calculation.
authors.affiliation: Departament de Quimica Fisica i Inorgànica, Universitat Rovira i Virgili, Marcel, lí Domingo s/n, E-43007, Tarragona, Spain.
authors.forename: Mariano
authors.initials: M
authors.lastname: Spivak
authors.forename: Celestino
authors.initials: C
authors.lastname: Angeli
authors.forename: Carmen J
authors.initials: CJ
authors.lastname: Calzado
authors.forename: Coen
authors.initials: C
authors.lastname: de Graaf
mesh_terms: D008280:Magnetics; D008958:Models, Molecular
keywords: NEVPT2; difference dedicated configuration interaction; magnetic coupling; multiconfigurational perturbation theory; transition metal complexes