Tailoring the donor moieties in TPA ‐based organic dyes for efficient photovoltaic, optical and nonlinear optical response properties

The current study reports tailoring the electronic donor structures of organic dyes to modify their optical and nonlinear optical (NLO) response properties. Five (5) tri‐phenyl amine (TPA) based Donor‐π‐Acceptor (D‐π‐A) organic dyes with the codes ICAA1 , ICAA2 , ICAA3 , ICAA4 , and ICAA5 were designed and investigated for their optical and NLO properties using quantum chemical methods. Optical and NLO properties of these dyes were studied by CAM‐B3LYP method and 6‐311G* basis set. The focus has been on the impact of adding secondary donors and shifting their substitutions at ortho ( o ), meta ( m ) and para ( p ) positions. Among all designed compounds, ICAA4 showed the highest amplitude of average third‐order NLO polarizability , which is calculated to be 1316 × 10 −36 esu. Time‐dependent Density Functional Theory (TD‐DFT) method was used to determine how a change in the position of the donor affected the excitation energy ( E g ) and NLO response properties. The findings showed that changing the position of the secondary donor results in a red shift among absorption spectra as well as the increase in their NLO responses. Complete process of intramolecular charge transfer (ICT) has been investigated in terms of different optical parameters such as frontier molecular orbitals (FMOs), molecular electrostatic potentials (MEPs), transition density matrix (TDMs), density of states (DOS), electron density difference (EDD), and natural bond orbital (NBO) analysis. Our calculations for study of ICT process indicate that p ‐position of methoxy group performs better among all other positions and even it has better NLO response properties than the compound with three collective methoxy groups. The calculated V oc values of all designed molecules range from 1.09 to 1.30, all of them are positive while their Δ G inject is found to be in the range of −0.87 to −1.79 eV indicating their decent potential for photovoltaic applications. The studied optical, NLO and photovoltaic parameters illustrated that ICAA1 to ICAA5 are appropriate molecules not only for NLO applications but also for efficient photovoltaic purposes.