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. © 2014 Wiley Periodicals, Inc. Taking into account the ionic state in the optimization procedure of the molecular orbitals results in slightly more delocalized magnetic orbitals, and hence, repairs the underestimation of the magnetic coupling commonly observed for multiconfigurational perturbation theory. Copyright © 2014 Wiley Periodicals, Inc.