title: Electronic and magnetic properties of DUT-8(Ni).
abstract: First principles calculations using density functional theory (DFT) have been performed to investigate the electronic and magnetic properties of DUT-8(Ni) (DUT - Dresden University of Technology). This flexible metal-organic framework (MOF) exists in two crystalline forms: DUT-8(Ni)open and DUT-8(Ni)closed. To identify the energetically favoured magnetic ordering, the density of states (DOS) and the energy difference between a low-spin (LS) and a high-spin (HS) coupling ΔELS-HS for those crystalline structures have been computed. Calculations on supercells have been carried out to include a variety of different magnetic couplings beyond a single unit cell. Several molecular model systems have been employed to further investigate the magnetic behaviour by introducing a diversity of chemical environments to the magnetic centers. The magnetic ground state of both crystalline structures has been found to be the low-spin state (S = 0). This low-spin ordering can be seen in the DOS as well as from ΔELS-HS calculations. Additionally, the calculations on the supercells confirm that the local character of the ordering (i.e. within the Ni dimers) is the most favoured one. However, the model systems indicate a change from the low-spin (S = 0) to a high-spin (S ≠ 0) ordering by introducing certain alterations into the chemical environment. Such alterations could be incorporated into the crystalline systems which should lead to similar results.
authors.affiliation: Technische Universität Dresden, Theoretical Chemistry, Germany. kai.trepte@chemie.tu-dresden.de.
authors.forename: Kai
authors.initials: K
authors.lastname: Trepte
authors.forename: Sebastian
authors.initials: S
authors.lastname: Schwalbe
authors.forename: Gotthard
authors.initials: G
authors.lastname: Seifert