Charge Transport and Optical Absorption Properties of Dibenzocoronene Tetracarboxdiimide Based Liquid Crystalline Molecules: A Theoretical Study.

Structure, optical absorption, and charge transport properties of dibenzocoronene tetracarboxdiimide (DCDI) based molecules were studied using electronic structure calculations. Based on the optimized neutral, cationic, and anionic geometries the ionized state properties, such as ionization potential, electron affinity, hole extraction potential, electron extraction potentials, and reorganization energy, were calculated. On the basis of the ground state geometry of the studied molecules, the absorption spectra were calculated using the time-dependent density functional theory (TDDFT) method at the PBE0/def-TZVP level of theory. It has been observed that the substitution of different functional groups significantly alters the absorption spectra of DCDI. The methoxy- (OCH3-) substituted DCDI molecule has a maximum absorption wavelength of 529 nm. The charge transport parameters, such as the charge transfer integral, spatial overlap integral, and the site energy, are calculated directly from the Kohn-Sham matrix elements. The reorganization energy for the presence of excess positive and negative charges and the charge transfer rate calculated from Marcus' theory were used to find the mobility of charge carriers. The computed results show that the mobility of charge carriers is strongly influenced by the functional groups present on the DCDI molecule. The effect of intermolecular structural fluctuations on charge transport properties was studied through molecular dynamics and Monte Carlo simulations based on the polaron hopping mechanism. The calculated charge carrier mobility shows that the cyano- (CN-) substituted DCDI molecules are having n-type semiconducting property while, methoxy- (OCH3-) and thiol- (SH-) substituted DCDI molecules exhibit ambipolar semiconducting properties.