Investigation of second-order NLO properties of novel 1,3,4-oxadiazole derivatives: a DFT study

In this study, we have developed four new chromophores (TM1-TM4) and performed quantum chemical calculations to explore their nonlinear optical properties. Our focus was on understanding the impact of electron-donating substituents on 1,3,4-oxadiazole derivative chromophores. The natural bond orbital analysis confirmed the interactions between donors and acceptors as well as provided insights into intramolecular charge transfer. We also estimated dipole moment, linear polarizability molecular electrostatic potential, UV-visible spectra, and first hyperpolarizability. Our results revealed that TM1 with a strong and stable electron-donating group exhibited high first hyperpolarizability (β) 293,679.0178 × 10^-34 esu. Additionally, TM1 exhibited a dipolar moment (μ) of 5.66 Debye and polarizability (α) of 110.62 × 10^-24 esu when measured in dimethyl sulfoxide (DMSO) solvent. Furthermore, in a benzene solvent, TM1 showed a low energy band gap of 5.33 eV by using the ωB97XD functional with a 6-311 +  + G(d, p) basis set. Moreover, our study of intramolecular charge transfers highlighted N, N dimethyl triphenylamine and carbazole as major electron-donating groups among the four 1,3,4-oxadiazole derivative chromophores. This research illustrates the potential applications of these organic molecules in photonics due to their versatile nature.

The molecules were individually optimized using different functionals, including APFD, B3LYP, CAM B3LYP, and ωB97XD combined with the 6-311 +  + G (d, p) basis set in Gaussian 16 software. These methods encompass long-range functionals such as APFD and B3LYP, along with long-range corrected functionals like CAM B3LYP and ωB97XD. The employed functionals of APFD, B3LYP, CAM B3LYP, and ωB97XD with the 6-311 +  + G (d,p) basis set were used to extract various properties such as geometrical structures, dipole moment, molecular electrostatic potential, and first hyperpolarizability through precise density functional theory (DFT). Additionally, TD-DFT was utilized for obtaining UV-visible spectra. All studies have been conducted in both gas and solvent phases.