Magnetic circular dichroism spectra of transition metal complexes calculated from restricted active space wavefunctions.

Abstract

First principles multiconfigurational restricted active space (RAS) self-consistent field (SCF) or configuration interaction (CI) approaches, augmented with a treatment of spin-orbit coupling by state interaction, were used to calculate the magnetic circular dichroism (MCD) , , and/or for closed- and open-shell transition metal complexes: PdCl42-, PdBr42-, AuCl4-, AuBr4-, MnO4-, CuCl42-, CuBr42-, and Fe(CN)63-. The were determined with a sum-over-states approach. It is shown that reasonably accurate MCD spectra can be obtained directly at a RAS level or at a RAS level augmented with corrections for the dynamic correlation. The sign and magnitude of the individual MCD terms can be unambiguously determined and assigned to particular electronic transitions.