The Electron-Vibrational Interaction in a Thiophene—Phenylene Cooligomer and Its Relationship to the Raman Spectrum

Electron-vibrational interactions play a key role in limiting charge mobility in organic semi-conductors. This paper reports a theoretical study of the electron—phonon interaction in the 5,5′-diphenyl-2,2′-bitiophene (PTTP) molecule, which belongs to the class of thiophene-phenylene cooligomers, which are of great interest for organic optoelectronics due to their electron-transport and luminescent properties; these results are compared with anthracene, which is a model organic semiconductor. The contributions of various vibrational modes to the reorganization energy of PTTP and the anthracene molecules are revealed and it is shown that these contributions correlate with the intensities of the corresponding bands in the Raman spectrum. In particular, it is found that for the PTTP molecule the so-called I-mode with a frequency of ∼1460 cm−1, which corresponds to collective vibration of atoms of all oligomer units, has the highest intensity in both spectra. These results indicate the promise of Raman spectroscopy for studying electron-vibrational interactions in organic semiconductors. Finally, the mobility of holes in PTTP and anthracene is estimated in the framework of the jump model and the reasons for their difference are analyzed. Based on these results, we propose some ways to reduce the electron-vibrational interaction in thiophene—phenylene cooligomers, which is important for the directional molecular design of organic semiconductors.