title: [Mo2(CN)11]:5- A detailed description of ligand-field spectra and magnetic properties by first-principles calculations.
abstract: An ab initio multiconfigurational approach has been used to calculate the ligand-field spectrum and magnetic properties of the title cyano-bridged dinuclear molybdenum complex. The rather large magnetic coupling parameter J for a single cyano bridge, as derived experimentally for this complex by susceptibility measurements, is confirmed to a high degree of accuracy by our CASPT2 calculations. Its electronic structure is rationalized in terms of spin-spin coupling between the two constituent hexacyano-monomolybdate complexes. An in-depth analysis on the basis of Anderson's kinetic exchange theory provides a qualitative picture of the calculated CASSCF antiferromagnetic ground-state eigenvector in the Mo dimer. Dynamic electron correlations as incorporated into our first-principles calculations by means of the CASPT2 method are essential to obtain quantitative agreement between theory and experiment.
authors.affiliation: Katholieke Universiteit Leuven, Department of Chemistry, Celestijnenlaan 200F, B-3001 Leuven, Belgium.
authors.forename: Marc F A
authors.initials: MF
authors.lastname: Hendrickx
authors.forename: S
authors.initials: S
authors.lastname: Clima
authors.forename: L F
authors.initials: LF
authors.lastname: Chibotaru
authors.forename: A
authors.initials: A
authors.lastname: Ceulemans