DFT Investigations on the Influence of Stacking on the Electronic Structure, Absorption, and Non-linear Optical Properties of 3,5-bis[4-(4-methylphenylcarbonyloxy)phenyl]-1,2,4-oxadiazole

Context: 1,2,4-Oxadiazole serves as a fundamental building block driving advancements across diverse scientific and technological arenas, contributing to the creation of innovative materials for various applications including devices, sensors, medications, agrochemicals, and biomedical instruments. Employing density functional theory (DFT) methods, we investigate the impact of different conformers of an oxadiazole substituted derivative, specifically 3,5-bis[4-(4-methylphenylcarbonyloxy)phenyl]-1,2,4-oxadiazole, in both monomeric and stacked configurations (dimeric and tetrameric). We analyze the electronic structures of various conformers, including assessment of HOMO-LUMO energy gaps, to detect the influence of diverse substituents and stacking arrangements. We have also explored the stability of stacked structure in explicit solvent environment. Additionally, we examine absorption spectra, non-linear optical properties, and electronic circular dichroism to evaluate the potential applications of these molecules in optoelectronic devices. Our calculations showed that all the conformers were thermodynamically stable within an energy difference of 2.64 kcal mol. The study also suggests possible application of the material in optical and electronic devices.

Methods: DFT calculations were carried out using the CAM-B3LYP and wB97XD functionals with a 6-31 + G* all-electron basis set, paired with the SCRF/PCM solvation model, implemented in the Gaussian 09 package. Equilibrium structure was achieved by performing NPT and NVT simulations using the Gromacs package.