Tuning the push–pull configuration for efficient second-order nonlinear optical properties in some chalcone derivatives

[Display omitted] •The potential of several push–pull chalcones as efficient NLO-phores is assessed.•NLO properties are calculated for different chalcone derivatives using DFT methods.•Chalcones with trimethoxypyren and nitro groups are found as efficient NLO-phores.•The structure-NLO property relationship has been extended to several experimental chalcones. Using the density functional theory methods, we effectively tune the second-order nonlinear optical (NLO) properties in some chalcone derivatives. Various unique push–pull configurations are used to efficiently enhance the intramolecular charge transfer process over the designed derivatives, which result in significantly larger amplitudes of the first hyperpolarizability as compared to their parent molecule. The ground state molecular geometries have been optimized using B3LYP/6-311G** level of theory. A variety of methods including B3LYP, CAM-B3LYP, PBE0, M06, BHandHLYP and MP2 are tested with 6-311G** basis set to calculate the first hyperpolarizability of parent system 1. The results of M06 are found closer to highly correlated MP2 method, which has been selected to calculate static and frequency dependent first hyperpolarizability amplitudes of all selected systems. At M06/6-311G** level of theory, the permanent electronic dipole moment (μtot), polarizability (α0) and static first hyperpolarizability (βtot) amplitudes for parent system 1 are found to be 5.139 Debye, 274a. u. and 24.22×10−30esu, respectively. These amplitudes have been significantly enhanced in designed derivatives 2 and 3. More importantly, the (βtot) amplitudes of systems 2 and 3 mount to 75.78×10−30 and 128.51×10−30esu, respectively, which are about 3 times and 5 times larger than that of their parent system 1. Additionally, we have extended the structure-NLO property relationship to several newly synthesized chalcone derivatives. Interestingly, the amplitudes of dynamic frequency dependent hyperpolarizability μβω (SHG) are also significantly larger having values of 366.72×10−48, 856.32×10−48 and 1913.46×10−48esu for systems 1–3, respectively, at 1400nm of incident laser wavelength. The dispersion behavior over a wide range of change in wavelength has also been studied adopting a range of wavelength from 1907 to 544nm. Thus, the present work realizes the potential of designed derivatives as efficient NLO-phores for modern NLO applications.