A cellular ligand-field model for ‘l-l’ spectral intensities

Abstract

A model for the calculation of the intensity distribution in ligand-field ‘l-l’ spectra is presented. The approach builds upon the eigenvectors of prior ligand-field analysis and incorporates the superposition of contributions associated with individual metal-ligand interactions in a complete complex. Local transition moments are parameterized by quantities {t _λ} which bear some resemblance to the {e _λ} of the cellular model of the ligand field itself. Equivalence between matrix elements of the electric-dipole operators acting within mixed-parity, local orbitals and of even-parity, effective transition-moment operators acting within pure l orbitals is exploited to construct a scheme that allows the computation of ‘l-l’ spectral intensities sequentially upon ligand-field diagonalization and within a similar basis of atomic eigenfunctions.