Electronic transitions in polymethine dyes involving local and delocalized levels

Autor: Olga V. Przhonska, Mykola P. Shandura, Yu.L. Bricks, M.O. Kudinova, O.D. Kachkovsky, Oleksandr O. Viniychuk, Svitlana M. Levchenko, Yu. P. Kovtun, Ye.M. Poronik, O.I. Tolmachev
Rok vydání: 2014
Předmět:
Zdroj: Journal of Molecular Structure. 1060:30-37
ISSN: 0022-2860
DOI: 10.1016/j.molstruc.2013.12.038
Popis: Several series of polymethine dyes containing terminal groups, which can generate the local levels close to the HOMO/LUMO energy gap, have been investigated by spectroscopic and quantum-chemical methods. The analysis of the obtained data has shown that the participation of the local levels in the electronic transitions leads to the appearance of the specific quasi-local transitions which differ from the transitions between delocalized molecular orbitals by their sensitivity to the length of the π-conjugated chromophore and to the chemical constitution of the terminal groups. These quasi-local transitions can be experimentally detected by measuring of the ordinary absorption spectra or by the excitation anisotropy spectra, in case when their low-intensive bands are covered by the intensive absorption band. In the unsymmetrical dyes, containing different terminal groups, the delocalized and quasi-local transitions can be mixed producing complicated absorption spectra with two comparatively intensive bands, and their shapes can be gradually transformed upon the lengthening of the π-conjugated chromophore.
Databáze: OpenAIRE