Di-μ-chloro-bis[dicarbonylpalladium(I)] molecular structure characterization by Hartree-Fock and local spin density methods

Abstract

Molecular electronic structure calculations of the experimental hinge and hypothetical planar molecular conformations of the title compound have been carried out. To obtain a reasonable description we have used restricted and unrestricted Hartree-Fock (HF); singlets and triplets configuration interaction and local spin density (LSD) followed by non local corrections. All our results for the experimental hinge conformation confirm a 3B ground state. For the planar conformation all methods, except LSD, predict 3B as the ground state. For the hinge and planar conformations a negative large Mulliken bond order is shown for the PdPd bond. This PdPd interaction is larger for the 3B state than for the 1A state. A dissociation of the molecule in hinge conformation is obtained when a geometry optimization of the 3B and 1A states is carried out. This dissociation is obtained with both the HF and the LSD methods. This last result is in agreement with the experimental observation of extremely low stability of the compound, together with the low yield of the synthesis.