Magnetostructural effects in ligand stabilized Pd13 clusters: A density functional theory study

We show computationally that ligation allows tuning of the magnetostructural properties of the Pd-13 cluster. The bare, phosphine and thiol capped clusters were investigated at the density functional level. The most stable conformers of the bare cluster are of high spin, septet and nonet and of distorted C-3v, C-s and I-h geometries. Ligation stabilizes the I-h geometry and quenches the high spin states, down to a triplet for Pd-13(PH3)(12) and to a quintet for Pd-13(SCH3)(12). The influence of the two capping systems on the magnetostructural properties of the ligated clusters is analyzed in connection with their different bonding properties. The mixed ligand species Pd-13(SCH3)(6)(PH3)(6) is also characterized. Due to the multiple energetically accessible spin states, unusual thermal behaviour of the average magnetic moment is predicted for these clusters.