Ab-initio and density functional theory (DFT) computational study of the effect of fluorine on the electronic, optical, thermodynamic, hole and electron transport properties of the circumanthracene molecule.

In this paper, a systematic study of the electronic, optical, thermodynamic, optoelectronic, and nonlinear optical properties with RHF, B3LYP, wB97XD and BPBE methods using the cc-pVDZ basis set have been described to investigate the influence of fluorine (F) atom, which is an electron donor, on the circumanthracene (C(40)H(16)). Global reactivity descriptors, hole and electron transport properties were also calculated and compared with other studies on the same molecule. DFT/B3LYP results show that the undoped C(40)H(16) molecule (Egap = 2.135 eV) and its fluorine-doped derivatives (C(40)F(16) and C(40)H(10)F(6)) are semiconducting materials. However, doping the C(40)H(16) molecule with the fluorine atom, partially or totally, favors the creation of a strong donor-acceptor system by considerably reducing its energy gap (Egap). The energy gap values of molecules doped using DFT/B3LYP method are 2.020 eV and 2.081 eV for the C(40)F(16) and C(40)H(10)F(6) molecules, respectively. These gap energies are below 3 eV, which favours the electronic properties of these molecules. They can be used to design organic solar cells. The nonlinear optical parameters were calculated and compared with those of urea. The values of βmol and μ calculated for C(40)F(16) and C(40)H(10)F(6) are higher than those of urea; this shows that these two materials have good nonlinear optical properties and therefore, are very good candidates for the design of optoelectronics and photonics devices. Futhermore, our results show that the perfluorination effect on the circumanthracene molecule increases the hole and electron reorganization energies, the vertical and adiabatic electron affinities and ionization energies, the optoelectronic and nonlinear optical properties, the transition excitation energy and the reactivity indices. The reorganization energies values suggest that these materials have promising transport properties. The natural bond orbital (NBO) analysis was also performed to determine the stability energy and charge delocalization in molecules. The theoretical results of the compounds studied in our work are in agreement with the experimental results. This confirms their molecular structures.