Extraction of Pure-electronic Transition Frequency and Chromophor Polymorphism from Diffuse Vibronic Spectra

Abstract

Background: The adiabatic approach and thermal population of starting state sublevels in vibronic transition at non degenerate combining states of molecular chromophores open ways to calculate pure-electronic transition frequency (combining states gap) individually from diffuse absorption or emission spectra. Results: Experimental data and the theory show, that the model fits to homogene chromophores at room and not low temperatures to escape degeneration and inhomogeneity. Side result of the approach is possibility to view inhomogeneity of chromophores or solvent site inhomogeneity. Conclusions: The approach is applied to vibronic spectra of molecular systems: molecules in different aggregate states, molecular crystals, color and F-centers, films and quantum dots. The trouble with the procedure is using wings of spectra, where the errors can be introduced by overlapping of impurities spectra and even by measurement inaccuracy.