X-ray photoelectron and quantum-chemical investigation of the electronic structure of palladium chloride

The results of an x-ray photoelectron investigation of the core levels and valence band of PdCl₂ have been presented. A theoretical interpretation has been formulated on the basis of calculations of the expanded Pd₆Cl₈ ⁴⁺ and Pd₆Cl₁₂ clusters by the X-scattered wave method and a band calculation of a one-dimensional PdCl₂]_n crystal. The proposed scheme for the electronic structure of PdCl₂ satisfactorily accounts for the features of the x-ray photoelectron spectra, including the presence of satellite lines due to many-electron excitation. The inadequacy of the single-sphere approximation in the framework of the model of PdCl₄ ^2– for the theoretical interpretation of the electronic structure has been noted, and the significant role of the covalent component of the Pd-Cl bonds in the formation of palladium chloride has been demonstrated. The results of the XPS investigation in conjunction with the quantum-chemical calculations makes it possible to examine the optical spectra and the x-ray absorption and emission spectra of PdCl₂ on a single basis.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 22, No. 4, pp. 409–418, July–August, 1986.