Photophysical properties and vibrational structure of ladder-type penta p-phenylene and carbazole derivatives based on SAC-CI calculations

The pi-conjugated ladder-type molecules constitute an attractive field of organic photoactive materials. In this work, the photophysical properties of ladder-type penta-p-phenylene (LPP) and carbazole derivatives (bisindenocarbazole and diindolocarbazole) have been investigated theoretically using the symmetry-adapted cluster-configuration interaction (SAC-CI) method. The equilibrium geometries in the ground (S (0)) and first excited (S (1)) states were calculated to be planar, and the excitation is delocalized over the molecules. SAC-CI/DZP calculations have been applied to the absorption and emission spectra of these molecules. The absorption spectra were well reproduced in both peak positions and the shape of the absorption bands. The strong absorption is attributed to the highest occupied molecular orbital to the lowest unoccupied molecular orbital (H-L) transition; however, in carbazoles, the H-1 -> L transition is located below the H-L transition. The vibrational structure in the S (0)-S (1) absorption band of LPP was analyzed by calculating the Franck-Condon (FC) factors based on the potential energy surfaces (PESs) along the normal coordinates that are relevant to the geometry change. The vibrational structure was well reproduced by the theoretical simulation. The C-C stretching mode dominantly contributes to the vibrational structure, while the breathing motion of the molecular frame does not influence the structure. The emission energies calculated by the SAC-CI method also agree well with the experimental values. The vibrational structure in the fluorescence band was also examined by the FC analysis; the theoretical spectrum is satisfactory for the two carbazoles, while the 0-0 transition is overestimated in LPP. In diindolocarbazole, the S (2) state has a large oscillator strength, while the S (1) state has a small oscillator strength.