Density-functional investigation of the excited state properties and the Jahn-Teller effect in [CrX6]3? (X=Cl?, Br?)

Abstract

The luminescence of [CrX6]3− X=Br−, Cl− has been studied through density functional theory (DFT) using both deMon and ADF codes. Multiplet energies4A2,2E,4T2, and4T1 have been expressed as energies of non-redundant single determinants and calculated as in Ref. [1]. The influence of the metal ligand distance on the multiplet energies has been investigated. Of particular interest to this work is the Jahn-Teller effect distortion. We found that the system moves to a more stable geometry when the axial bond length is compressed and the equatorial one elongated in agreement with the experimental value.