Transferability of empirical crystal-field parameters of Ni(II) complexes of different symmetries

• Published in: Journal of solid state chemistry Vol. 44; no. 3; pp. 298 - 306
• Main Authors: Beltrán, F.Gómez, Sordo, J.A., Pueyo, L.
• Format: Journal Article
• Language: English
• Published: Elsevier Inc 01.01.1982
• ISSN: 0022-4596; 1095-726X
• DOI: 10.1016/0022-4596(82)90377-2

A method of systematic linearization of the crystal-field matrices appropriate for obtaining empirical parameters of transition metal complexes of any symmetry is presented and applied to forty complexes of Ni 2+ of O h and D 4 h symmetries. The method is a generalization of that proposed by L. Pueyo, M. Bermejo, and J. W. Richardson ( J. Solid State Chem. 31, 217 (1980)) for complexes of O h symmetry and incorporates the spin-orbit coupling in a very simple manner. Using this method, classical parameters, such as 10 Dq, and punctual quantities, such as the ligand perturbing charges q i , were obtained for these complexes. The former are transferable within 10% if (a) there are not big changes in the metal-ligand distances and (b) the chemical environments of the ligand atoms are comparable. However, the punctual parameters show variations of 20% or more. Electronic repulsion integrals seem to be nicely transferable by means of addition rules based on the hypothesis of isotropic repulsion in the low-symmetry field. Since one of the fitting parameters is a scaling factor of the R nl ( r) metal function, the process of optimization generates an empirical representation, R nl ( λr), of the locally perturbed metallic state.