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

Abstract

We show computationally that ligation allows tuning of the magnetostructural properties of the Pd₁₃ 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 Pd₁₃(PH₃)₁₂ and to a quintet for Pd₁₃(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 Pd₁₃(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.