title: Electronic structure and molecular properties of the heptacyanorhenate [Re(CN)7]3- and [Re(CN)7]4- complexes.
abstract: We report scalar relativistic and Dirac scattered wave (DSW) calculations on the heptacyanorhenate [Re(CN)7](3-) and Re(CN)7(4-) complexes. Both the ground and lowest excited states of each complex split by spin-orbit interaction by about 0.3 eV. The calculated molecular electronegativities chi indicate that the open-shell complex is less reactive than the closed-shell complex, in agreement with experimental observations. The calculations indicate that the ground state spin density is highly anisotropic and that spin-orbit effects are responsible for the magnetic anisotropy of the molecular g tensor of the Re(CN)7(3-) complex. The calculated optical electronic transitions for both complexes with a polarizable continuum model using a time-dependent density functional (TDDFT)/B3LYP formalism are in reasonable agreement with those observed in the absorption spectrum.
authors.affiliation: Departamento de Ciencias Químicas, Universidad Andrés Bello, República 275, Santiago, Chile.
authors.forename: Jorge
authors.initials: J
authors.lastname: David
authors.forename: Fernando
authors.initials: F
authors.lastname: Mendizábal
authors.forename: Ramiro
authors.initials: R
authors.lastname: Arratia-Pérez