How does hybrid bridging core modification enhance the nonlinear optical properties in donor‐π‐acceptor configuration? A case study of dinitrophenol derivatives

Abstract

This study spotlights the fundamental insights about the structure and static first hyperpolarizability (β) of a series of 2,4-dinitrophenol derivatives (1-5), which are designed by novel bridging core modifications. The central bridging core modifications show noteworthy effects to modulate the optical and nonlinear optical properties in these derivatives. The derivative systems show significantly large amplitudes of first hyperpolarizability as compared to parent system 1, which are 4, 46, 66, and 90% larger for systems 2, 3, 4, and 5, respectively, at Moller-Plesset (MP2)/6-31G* level of theory. The static first hyperpolarizability and frequency dependent coupled-perturbed Kohn-Sham first hyperpolarizability are calculated by means of MP2 and density functional theory methods and compared with respective experimental values wherever possible. Using two-level model with full-set of parameters dependence of transition energy (ΔΕ), transition dipole moment (μ(0)) as well as change in dipole moment from ground to excited state (Δμ), the origin of increase in β amplitudes is traced from the change in dipole moment from ground to excited state. The causes of change in dipole moments are further discovered through sum of Mulliken atomic charges and intermolecular charge transfer spotted in frontier molecular orbitals analysis. Additionally, analysis of conformational isomers and UV-Visible spectra has been also performed for all designed derivatives. Thus, our present investigation provides novel and explanatory insights on the chemical nature and origin of intrinsic nonlinear optical (NLO) properties of 2,4-dinitrophenol derivatives.

An investigation on the key features of a D–π–A type novel chalcone derivative for opto-electronic applications

“…The FF approach has been widely used to calculate the rst hyperpolarizability of numerous chemical systems and has provided very consistent results when compared with the experimental data. 52,53 Herein, we have applied various methods, including B3LYP, HF, range separated hybrid functionals, such as CAM-B3LYP and wb97xd, and long range corrected LC-BLYP at the 6-31G* basis set for calculating the dipole moment and rst hyperpolarizability, and compared them with each other. In general, in the FF approach, a static electric eld (F) is applied and the energy (E) is expressed by the following equation:…”

NLO Properties of 2‐Napthol Monoazo Disperse Dyes by DFT and Z‐Scan Technique – A Detailed Study

“…The theoretically observed values of first‐order hyperpolarizability (β) and second‐order hyperpolarizability (γ) for 2‐napthol azo dyes 1–4 are larger than the values for hyperpolarizability of urea . Moreover, the β and γ values of these dyes were compared with the reported donor‐π‐acceptor dyes . We found that β and γ values of these dyes are competes with the reported donor‐π‐acceptor dyes supplementary information (Table S30).…”

Effect of Polymerization on the Charge-Transfer Mechanism in the One (Two)-Photon Absorption Process of D–A-Type Triphenylamine Derivatives

“…TPA is a typical third-order NLO absorption phenomenon. To compare the effect of polymerization on the third-order NLO properties, DFT/B3LYP/6-31+G­(d) is utilized to calculate the second static hyperpolarizabilities (γ ijkl ) − using Gaussian 09.…”