title: Magnetic coupling constants and vibrational frequencies by extended broken symmetry approach with hybrid functionals.
abstract: The description of the electronic structure and magnetic properties of multi-centers transition metal complexes, especially of mixed-valence compounds, still represents a challenge for density functional theory (DFT) methods. The energies and the geometries of the correctly symmetrized low-spin ground state are estimated using the Heisenberg-Dirac-van Vleck spin Hamiltonian within the extended broken symmetry method introduced by Marx and co-workers [Nair et al., J. Chem. Theory Comput. 4, 1174-1188 (2008)]. In the present work we extend the application of this technique, originally implemented using the DFT+U scheme, to the use of hybrid functionals, investigating the ground-state properties of di-iron and di-manganese compounds. The calculated magnetic coupling and vibrational properties of ferredoxin molecular models are in good agreements with experimental results and DFT+U calculations. Six different mixed-valence Mn(III)-Mn(IV) compounds have been extensively studied optimizing the geometry in low-spin, high-spin, and broken-symmetry states and with different functionals. The magnetic coupling constants calculated by the extended broken symmetry approach using B3LYP functional presents a remarkable agreement with the experimental results, revealing that the proposed methodology provides a consistent and accurate DFT approach to the electronic structure of multi-centers transition metal complexes.
authors.affiliation: Physics Department, La Sapienza-University of Rome, Rome, Italy.
authors.forename: D
authors.initials: D
authors.lastname: Bovi
authors.forename: L
authors.initials: L
authors.lastname: Guidoni
mesh_terms: D007501:Iron / Q000737:chemistry; D060328:Magnetic Phenomena; D008345:Manganese / Q000737:chemistry; D009942:Organometallic Compounds / Q000737:chemistry*; D011789:Quantum Theory; D014732:Vibration
chemical_list: D009942:Organometallic Compounds; D008345:Manganese; D007501:Iron