Quantum computational study of non-linear optical properties of some phenanthrene derivatives

Non-linear optical (NLO) behavior of some phenanthrene-based organic molecules is studied using quantum computational MP2 and B3LYP methods with cc-pVDZ basis set. The design of these molecules is based on possible intramolecular charge transfer between electron donor and electron acceptor groups via an aromatic bridge. The -NO₂, -CN, -CF₃, -C(CF₃)C(CF₃)₂, -SO₃H and -C(CN)C(CN)₂ acceptors and the -NH₂, -N(CH₃)₂ and pyrrolidinyl donors have been considered. The HOMO and LUMO energies, polarizabilities and first hyperpolarizabilities are calculated for the optimized structures both in the gas phase and in the conductor-like polarizable continuum model (CPCM) of different solvents. Moreover, the energies of the vertical transitions in the UV-Vis range having large oscillator strengths and their corresponding adiabatic transition energies are calculated using TD-DFT-B3LYP/cc-pVDZ method. Also, UV-Vis and infrared spectra are simulated for these designed molecules. Results show that these phenanthrene derivatives have generally very good NLO behavior. Also, NLO properties are enhanced when (-C(CN)C(CN)₂ & -NH₂) and (-NO₂ & pyrrolidinyl) pairs of (acceptor & donor) groups are used. The approach adopted in the present quantum computational study can be used for similar studies for better description and understanding of the NLO responses of the electron donor-bridge-acceptor systems with π-conjugated bridges.