ISSN:
1600-5740
Source:
Crystallography Journals Online : IUCR Backfile Archive 1948-2001
Topics:
Chemistry and Pharmacology
,
Geosciences
,
Physics
Notes:
Aspherical distributions of the d electrons in dipotassium palladium hexachloride, K2[PdCl6], and dipotassium platinum hexachloride, K2[PtCl6], crystals were analyzed by theoretical calculations. Hartree–Fock and configuration interaction calculations were performed for [PdCl6]2− and [PtCl6]2− with and without taking into account the Madelung potentials, using a model potential method. The major relativistic effects were incorporated in the model potentials for Pd and Pt. The deformation-density maps calculated were similar to those given by the X-ray diffraction method. The theoretical result suggested that the positive peaks on the threefold axes and the negative peaks on the metal—Cl bond axis correspond to the excess d electrons (4d of Pd and 5d of Pt) in the t2g (dxy, dxz, dyz) orbitals and the electron deficiency in the eg (dz2,dx2−y2) orbitals, respectively. The positive and negative peak heights were calculated to be +1.8 and −0.8 e Å−3 for [PdCl6]2− and +1.2 and −0.6 e Å−3 for [PtCl6]2−. The effective charges and effective radii of Pd and Pt, and the number of electrons in the t2g, eg and t1u orbitals, were calculated by direct integration. The effects of the Madelung potential and electron correlation on the charge distributions of [PdCl6]2− and [PtCl6]2− were also analyzed.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1107/S010876819501202X
