Enhancing NLO performance by utilizing tyrian purple dye as donor moiety in organic DSSCs with end capped acceptors: A theoretical study

A series of new organic dyes (T1-T6) with nonfullerene acceptors have been theoretically designed around the chemical structure of tyrian purple (T) natural dye. For their ground state energy parameters, all the molecular geometries of those dyes were optimized by density functional theory (DFT) at its Becke, 3-parameter, Lee–Yang–Parr (B3LYP) level of theory with 6–31G+(d,p) basis sets. When benchmarking against several long range and range separated levels of theory, the Coulomb attenuated B3LYP (CAM-B3LYP) produced most accurate absorption maxima (λmax) value to that of T so it was further employed for further Time dependent DFT (TD-DFT) calculations. Frontier molecular orbitals (FMOs) with natural bond orbital (NBO) studies were used to study their intra molecular charge transfer (ICT). All of the dyes had their energy gaps (Eg) values between their FMOs to range around 0.96–3.39 eV, whereas the starting reference dye had an Eg of 1.30 eV. Their ionization potential (IP) values were ranged to be 3.07–7.25 eV which indicated their nature to loss electrons. The λ max in chloroform was marginally red-shifted with a value 600–625 from T (580 nm). The dye T6 showed its highest linear polarizability (), and first and second order hyperpolarizabilities (β and γ). The synthetic experts can find the present research to design finest NLO materials for current and future uses. [Display omitted] •A study to highlight the importance of theoretical modeling to improve DSSCs performance.•Efficient utilization of Tyrian purple natural dye as a donor moiety.•Exploration of nonlinear optical (NLO) performance for new dyes.•The results shed insights into the design and optimization of organic DSSCS.