Analyses of Vibrational Progressions in Luminescence Spectra of Platinum‐Group d6Complexes

Abstract

AbstractLow temperature (10 K) luminescence spectra of powder samples and single crystals of various Rh(III), Ir(III), and Pt(IV) complexes have been recorded. Some of these show vibrational fine structure which is explained by several progressions arising from different promoting modes. Band analyses carried out by decomposing the emission profile into a series of lorentzian or gaussian distributions lead to accepting mode frequencies which match frequencies in vibrational spectra. By comparing intensity distributions in the progressions with theoretical line shape functions from recent vibronic theories, some optical and geometrical parameters pertaining to the excited electronic states (potential minima shifts, changes in oscillator frequencies with respect to the ground state) have been calculated. For this analysis the quality of the vibrational resolution is of importance. Broad band vibronic spectra which cannot be resolved at low temperature can also be used to a certain degree for determining excited state properties. The results obtained from simple models seem to agree well with the data obtained from the narrow line spectra.